BTEX REMOVAL FROM PRODUCED WATER USING …of BTEX from produced water. The long-term effectiveness...

BTEX REMOVAL FROM PRODUCED WATER USING SURFACTANT-MODIFIED ZEOLITE

by

John Michael Ranck

Submitted in Partial Fulfillment of

the Requirements for the Degree of

Master of Science in Hydrology

New Mexico Institute of Mining and Technology

Socorro, New Mexico

December 2003

ABSTRACT

Produced water contains large amounts of various hazardous organic compounds

such as benzene, toluene, ethylbenzene, and xylenes (BTEX). With increasing

regulations governing disposal of this water, low-cost treatment options are necessary.

This study evaluated the effectiveness of surfactant-modified zeolite (SMZ) for removal

of BTEX from produced water. The long-term effectiveness of SMZ for BTEX removal

was investigated along with how sorption properties change with long-term use. The

results from these investigations showed that SMZ successfully removes BTEX from

produced water, and that SMZ can be regenerated via air-sparging without loss of

sorption capacity. The BTEX compounds break through laboratory columns in order of

decreasing water solubility and of increasing Kow. The most soluble compound, benzene,

began to elute from the column at 8 pore volumes (PV), while the least soluble

compounds, ethylbenzene and xylenes, began to elute at 50 PV. After treating 4500 pore

volumes of water in the column system over 10 sorption/regeneration cycles, no

significant reduction in sorption capacity of the SMZ for BTEX was observed. The mean

Kd from these column experiments ranged from a low value of 18.3 L/kg for benzene to

the highest value of 95.0 L/kg for p-&m-xylene. Batch sorption experiments confirmed

the column results showing no significant loss of capacity for BTEX sorption after 10

sorption/regeneration cycles, although the batch Kd values were consistently lower than

Kds from the column experiments. Batch Kds ranged from a low of 6.71 L/kg for benzene

to a high of 39.4 L/kg for o-xylene.

Laboratory columns were upscaled to create a field-scale SMZ treatment system.

The field-scale system was tested at a produced water treatment facility near Wamsutter,

Wyoming. We observed greater sorption of BTEX in field columns tests than predicted

from laboratory column studies. In the field column, initial benzene breakthrough

occurred at 10 PV and toluene breakthrough began at 15 PV, and no breakthrough of

ethylbenzene or xylenes occurred throughout the 80 PV experiment. These results, along

with the low cost of SMZ, indicate that SMZ has a potential role in a cost-effective

produced water treatment system.

ii

ACKNOWLEDGEMENTS

I would like to thank the many people who have assisted me during my time at

New Mexico Tech. To those who have helped with homework, listened to me bouncing

ideas and frustrations around, helped out in the lab, and helped take my mind off of

school sometimes; thank you. Special thanks go to Dr. Robert Bowman for introducing

me to SMZ and assisting me all along the way. I would like to recognize Sarah

Loughney for her help with sampling columns and keeping the lab in order. Thanks to

Dr. E. Jeri Sullivan and Jim Smith for training me and helping me with the SEM analysis.

In addition, I would like to thank Fei Zhang and Alana Fuierer for helping me during my

first few weeks of learning the necessary experimentation and analysis techniques.

Thanks to all of my friends and family who have supported and encouraged me,

whether it be from here in Socorro or from across the country.

iii

TABLE OF CONTENTS

Page

TABLE OF CONTENTS................................................................................................... iii

LIST OF FIGURES ............................................................................................................ v

LIST OF TABLES............................................................................................................. vi

LIST OF APPENDICES FIGURES ................................................................................. vii

LIST OF APPENDICES TABLES..................................................................................... x

INTRODUCTION .............................................................................................................. 1

PAPER ENTITLED "BTEX REMOVAL FROM PRODUCED WATER USING SURFACTANT-MODIFIED ZEOLITE" .......................................................................... 2

ABSTRACT............................................................................................................ 2

INTRODUCTION .................................................................................................. 4

MATERIALS AND METHODS............................................................................ 8

RESULTS AND DISCUSSION........................................................................... 17

CONCLUSIONS................................................................................................... 25

ACKNOWLEDGEMENTS.................................................................................. 25

APPENDIX I. REFERENCES. ........................................................................... 26

APPENDIX II. NOTATION ............................................................................... 29

FIGURE CAPTIONS............................................................................................ 34

INTRODUCTION TO APPENDICES............................................................................. 42

APPENDIX A . PRELIMINARY LAB COLUMN DISCUSSION AND DATA........... 44

iv

APPENDIX B . COLUMN FLOW PROPERTIES, SMZ LOSS, AND SCANNING ELECTRON MICROSCOPY INVESTIGATION OF SMZ PARTICLE BREAKDOWN...................................................................................... 59

APPENDIX C . LABORATORY COLUMN BTC DATA.............................................. 79

APPENDIX D . BATCH EXPERIMENT RESULTS.................................................... 132

APPENDIX E . FIELD COLUMN METHODS AND RESULTS ................................ 146

APPENDIX F . ADDITIONAL ORGANIC MATERIAL IN PRODUCED WATER.. 153

APPENDIX G . APPLICABLE PRODUCED WATERS FOR AN SMZ TREATMENT SYSTEM.............................................................................................. 165

v

LIST OF FIGURES

Page

Figure 1. Observed and fitted (Eq. 2) breakthrough curves for tritiated water in Column 10A....................................................................................................... 35

Figure 2. Observed and fitted BTEX breakthrough curves on virgin SMZ

(Column 10A). The lines were based on the best fit of eq. 10 to the observed data, as described in the text. .............................................................. 36

Figure 3. BTCs of benzene and p-&m-xylene in Columns 10A and 10B for (a)

virgin SMZ and (b) during the fifth sorption cycle in columns 10A and 10B. .................................................................................................................... 37

Figure 4. (a) Benzene BTCs for Column 10A over 10 sorption/regeneration cycles

and (b) p-&m-xylene BTCs for Column 10A over 10 sorption/regeneration cycles. ............................................................................. 38

Figure 5. Cumulative masses of benzene, toluene, and p-&m-xylene removed

relative to masses sorbed during first regeneration in Column 10A.................. 39 Figure 6. Comparison of benzene and toluene BTC for virgin SMZ in lab column

10A and field column......................................................................................... 40 Figure 7. Benzene and toluene breakthrough on virgin and regenerated SMZ in

field column. ...................................................................................................... 41

vi

LIST OF TABLES

Page

Table 1. Analysis of produced water used in laboratory experiments. ............................. 31

Table 2. Dimensions and operating parameters for field and laboratory columns. .......... 32

Table 3. Mean Kd values determined by laboratory column and batch experiments. Standard deviations are shown in parentheses. “n” indicates the number of measurements for each mean. ..................................... 33

vii

LIST OF APPENDICES FIGURES

Page Appendix Figure B-1. Observed and fitted (Eq. 2) breakthrough curves for

tritiated water in Column 10B....................................................... 61 Appendix Figure B-2. Observed and fitted (Eq. 2) breakthrough curves for

tritiated water in Column 5A. ....................................................... 62 Appendix Figure B-3. Observed and fitted (Eq. 2) breakthrough curves for

tritiated water in Column 5B......................................................... 63 Appendix Figure B-4. SEM image of virgin SMZ (35X)................................................. 70 Appendix Figure B-5. SEM image of virgin SMZ (190X). Large particle in

upper-center is quartz.................................................................... 71 Appendix Figure B-6. SEM image of virgin SMZ (4500X)............................................. 72

Appendix Figure B-7. SEM image of Column 5A SMZ (35X). ...................................... 73

Appendix Figure B-8. SEM image of Column 5A SMZ (190X). .................................... 74

Appendix Figure B-9. SEM image of Column 5A SMZ (4500X). .................................. 75

Appendix Figure B-10. SEM image of Column 10B SMZ (35X).................................... 76

Appendix Figure B-11. SEM image of Column 10B SMZ (190X).................................. 77

Appendix Figure B-12. SEM image of Column 10A SMZ (4500X). .............................. 78

Appendix Figure C-1. Toluene BTCs for Column 10A over 10 sorption/regeneration cycles. ........................................................ 81

Appendix Figure C-2. Ethylbenzene BTCs for Column 10A over 10

sorption/regeneration cycles. ........................................................ 82 Appendix Figure C-3. o-xylene BTCs for Column 10A over 10

sorption/regeneration cycles. ........................................................ 83

viii

Appendix Figure C-4. Benzene BTCs for Column 10B over 10

sorption/regeneration cycles. ........................................................ 84 Appendix Figure C-5. Toluene BTCs for Column 10B over 10

sorption/regeneration cycles. ........................................................ 85 Appendix Figure C-6. Ethylbenzene BTCs for Column 10B over 10

sorption/regeneration cycles. ........................................................ 86 Appendix Figure C-7. p-&m-xylene BTCs for Column 10B over 10

sorption/regeneration cycles. ........................................................ 87 Appendix Figure C-8. o-xylene BTCs for Column 10B over 10

sorption/regeneration cycles. ........................................................ 88 Appendix Figure D-1. Benzene sorption isotherm for (a) virgin SMZ; (b)

Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ............ 133 Appendix Figure D-2. Toluene sorption isotherm for (a) virgin SMZ; (b) Columns

5A/5B SMZ; and (c) Columns 10A/10B SMZ. .......................... 134 Appendix Figure D-3. Ethylbenzene sorption isotherm for (a) virgin SMZ; (b)

Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ............ 135 Appendix Figure D-4. p-&m-xylene sorption isotherm for (a) virgin SMZ; (b)

Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ............ 136 Appendix Figure D-5. o-xylene sorption isotherm for (a) virgin SMZ; (b)

Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ............ 137 Appendix Figure E-1. Observed BTEX breakthrough on virgin SMZ in smaller

field column. ............................................................................... 148 Appendix Figure F-1. PID measurements with BTEX BTCs on virgin SMZ in

smaller field column. .................................................................. 158

Appendix Figure F-2. PID measurements with BTEX BTCs on virgin SMZ in larger field column...................................................................... 159

ix

Appendix Figure F-3. PID measurements with BTEX BTCs on regenerated SMZ in larger field column.................................................................. 160

x

LIST OF APPENDICES TABLES

Page Appendix Table A-1. BTEX BTC data on virgin SMZ in preliminary lab column. ........ 46

Appendix Table A-2. Benzene removal data.................................................................... 48

Appendix Table A-3. Toluene removal data..................................................................... 50

Appendix Table A-4. Ethylbenzene removal data............................................................ 52

Appendix Table A-5. p-&m-xylene removal data ............................................................ 54

Appendix Table A-6. o-xylene removal data.................................................................... 56

Appendix Table A-7. BTEX BTC data for preliminary lab column with regenerated SMZ........................................................................... 58

Appendix Table B-1. Hydrodynamic properties of laboratory columns before

sorption cycles. ............................................................................. 60 Appendix Table B-2. Tritium breakthrough data for virgin SMZ. ................................... 64

Appendix Table B-3. Hydrodynamic properties of laboratory columns after sorption cycles. ............................................................................. 65

Appendix Table B-4. Tritium breakthrough data after sorption cycles. ........................... 66

Appendix Table C-1. Data for BTEX BTC 1 from Column 10A..................................... 89






xi




Appendix Table C-10. Data for BTEX BTC 10 from Column 10A................................. 98

Appendix Table C-11. Data for BTEX BTC 1 from Column 10B................................... 99

Appendix Table C-12. Data for BTEX BTC 2 from Column 10B................................. 100








Appendix Table C-20. Data for BTEX BTC 10 from Column 10B............................... 108

Appendix Table C-21. BTEX removal data from Column 10A during first sparging cycle. ............................................................................ 109

Appendix Table C-22. BTEX removal data from Column 10A during second

sparging cycle. ............................................................................ 110 Appendix Table C-23. BTEX removal data from Column 10A during third

sparging cycle. ............................................................................ 111 Appendix Table C-24. BTEX removal data from Column 10A during fourth

sparging cycle. ............................................................................ 112

xii

Appendix Table C-25. BTEX removal data from Column 10A during fifth sparging cycle. ............................................................................ 113

Appendix Table C-26. BTEX removal data from Column 10A during sixth

sparging cycle. ............................................................................ 114 Appendix Table C-27. BTEX removal data from Column 10A during seventh

sparging cycle. ............................................................................ 115 Appendix Table C-28. BTEX removal data from Column 10A during eighth

sparging cycle. ............................................................................ 116 Appendix Table C-29. BTEX removal data from Column 10A during ninth

sparging cycle. ............................................................................ 117 Appendix Table C-30. BTEX removal data from Column 10A during tenth

sparging cycle. ............................................................................ 118 Appendix Table C-31. BTEX removal data from Column 10B during first

sparging cycle. ............................................................................ 119 Appendix Table C-32. BTEX removal data from Column 10B during second

sparging cycle. ............................................................................ 120 Appendix Table C-33. BTEX removal data from Column 10B during third

sparging cycle. ............................................................................ 121 Appendix Table C-34. BTEX removal data from Column 10B during fourth

sparging cycle. ............................................................................ 122 Appendix Table C-35. BTEX removal data from Column 10B during fifth

sparging cycle. ............................................................................ 123 Appendix Table C-36. BTEX removal data from Column 10B during sixth

sparging cycle. ............................................................................ 124 Appendix Table C-37. BTEX removal data from Column 10B during seventh

sparging cycle. ............................................................................ 125 Appendix Table C-38. BTEX removal data from Column 10B during eighth

sparging cycle. ............................................................................ 126

xiii

Appendix Table C-39. BTEX removal data from Column 10B during ninth

sparging cycle. ............................................................................ 127 Appendix Table C-40. BTEX removal data from Column 10B during tenth

sparging cycle. ............................................................................ 128 Appendix Table C-41. Kd, Mass sorbed, mass removed, and cumulative mass

remaining for BTEX compounds on Column 10A. .................... 129 Appendix Table C-42. Kd, Mass sorbed, mass removed, and cumulative mass

remaining for BTEX compounds on Column 10B. .................... 130 Appendix Table C-43. CXTFIT 2.1 calculations used to create manuscript Figure

2................................................................................................... 131 Appendix Table D-1. Benzene sorption on virgin SMZ................................................. 138

Appendix Table D-2. Benzene sorption on Column 5A/5B SMZ.................................. 138

Appendix Table D-3. Benzene sorption on Column 10A/10B SMZ.............................. 139

Appendix Table D-4. Toluene sorption on virgin SMZ. ................................................ 139

Appendix Table D-5. Toluene sorption on Column 5A/5B SMZ. ................................. 140

Appendix Table D-6. Toluene sorption on Column 10A/10B SMZ. ............................. 140

Appendix Table D-7. Ethylbenzene sorption on virgin SMZ......................................... 141

Appendix Table D-8. Ethylbenzene sorption on Column 5A/5B SMZ.......................... 141

Appendix Table D-9. Ethylbenzene sorption on Column 10A/10B SMZ...................... 142

Appendix Table D-10. p-&m-xylene sorption on virgin SMZ. ...................................... 142

Appendix Table D-11. p-&m-xylene sorption on Column 5A/5B SMZ. ....................... 143

Appendix Table D-12. p-&m-xylene sorption on Column 10A/10B SMZ. ................... 143

Appendix Table D-13. o-xylene sorption on virgin SMZ............................................... 144

xiv

Appendix Table D-14. o-xylene sorption on Column 5A/5B SMZ................................ 144

Appendix Table D-15. o-xylene sorption on Column 10A/10B SMZ............................ 145

Appendix Table E-1. Data for BTEX BTC on virgin SMZ in larger field column........ 149

Appendix Table E-2. Data for BTEX BTC on regenerated SMZ in larger field column......................................................................................... 150

Appendix Table E-3. Data for BTEX BTC on virgin SMZ in smaller field

column......................................................................................... 151 Appendix Table E-4. BTEX removal data from 14-inch field column during air

sparging....................................................................................... 152 Appendix Table F-1. TPH and semi-volatile analysis of untreated produced water

collected during field testing (only noting compounds present above detectable limits).................................................. 153

Appendix Table F-2. TOC analysis of produced water used in laboratory column

experiments. ................................................................................ 155 Appendix Table F-3. Semi-volatile breakthrough at 2.4 PV from smaller field

column......................................................................................... 156 Appendix Table F-4. PID measurements recorded on virgin SMZ in smaller field

column......................................................................................... 161 Appendix Table F-5. PID measurements recorded on virgin SMZ in larger field

column......................................................................................... 162 Appendix Table F-6. PID measurements recorded on regenerated SMZ in larger

field column. ............................................................................... 163

1

INTRODUCTION

This document is the result of a thesis project and contains a journal article and

supporting appendices. The thesis project partially fulfills the requirements for the

Degree of Master of Science in Hydrology at the New Mexico Institute of Mining and

Technology. The study evaluated the use of surfactant-modified zeolite for removal of

benzene, toluene, ethylbenzene, and xylenes from produced water. The objectives of the

study were to evaluate the long-term effectiveness of surfactant-modified zeolite to

remove these compounds from produced water, investigate how the sorption

characteristics of surfactant-modified zeolite change with progressive sorption and

regeneration cycles, and to evaluate our ability to predict results in a field system by

scaling from a laboratory system.

The following manuscript, entitled “BTEX Removal from Produced Water Using

Surfactant-Modified Zeolite,” was prepared for submission to the Journal of

Environmental Engineering, and follows the editorial guidelines set by the publisher

(American Society of Civil Engineers). The article presents the results of laboratory

column and batch experiments and field column experiments that were designed to fulfill

the objectives stated above.

The appendices contain information on preliminary and unreported studies, more

detailed descriptions of experimental procedures, and the results from the experiments I

have performed.

2

BTEX REMOVAL FROM PRODUCED WATER USING SURFACTANT-

MODIFIED ZEOLITE

J. Michael Ranck1, Robert S. Bowman2, Jeffrey L. Weeber3, Lynn E. Katz4, and Enid J.

Sullivan5

ABSTRACT

Produced water contains large amounts of various hazardous organic compounds

such as benzene, toluene, ethylbenzene, and xylenes (BTEX). With increasing

regulations governing disposal of this water, low-cost treatment options are necessary.

This study evaluated the effectiveness of surfactant-modified zeolite (SMZ) for removal

of BTEX from produced water. The long-term effectiveness of SMZ for BTEX removal

was investigated along with how sorption properties change with long-term use. The

results from these investigations showed that SMZ successfully removes BTEX from

produced water, and that SMZ can be regenerated via air-sparging without loss of

sorption capacity. The BTEX compounds break through laboratory columns in order of

decreasing water solubility and of increasing Kow. The most soluble compound, benzene,

began to elute from the column at 8 pore volumes (PV), while the least soluble

compounds, ethylbenzene and xylenes, began to elute at 50 PV. After treating 4500 pore

volumes of water in the column system over 10 sorption/regeneration cycles, no

1 Department of Earth and Environmental Science, New Mexico Tech, Socorro, NM 87801. 2 Department of Earth and Environmental Science, New Mexico Tech, Socorro, NM 87801 (corresponding author). E-mail: [email protected] 3 Department of Civil Engineering, University of Texas-Austin, Austin, TX 78712. 4 Department of Civil Engineering, University of Texas-Austin, Austin, TX 78712. 5 Los Alamos National Laboratory, RRES Division, Los Alamos, NM 87545.

3

significant reduction in sorption capacity of the SMZ for BTEX was observed. The mean

Kd from these column experiments ranged from a low value of 18.3 L/kg for benzene to

the highest value of 95.0 L/kg for p-&m-xylene. Batch sorption experiments confirmed

the column results showing no significant loss of capacity for BTEX sorption after 10

sorption/regeneration cycles, although the batch Kd values were consistently lower than

Kds from the column experiments. Batch Kds ranged from a low of 6.71 L/kg for benzene

to a high of 39.4 L/kg for o-xylene.

Laboratory columns were upscaled to create a field-scale SMZ treatment system.

The field-scale system was tested at a produced water treatment facility near Wamsutter,

Wyoming. We observed greater sorption of BTEX in field columns tests than predicted

from laboratory column studies. In the field column, initial benzene breakthrough

occurred at 10 PV and toluene breakthrough began at 15 PV, and no breakthrough of

ethylbenzene or xylenes occurred throughout the 80 PV experiment. These results, along

with the low cost of SMZ, indicate that SMZ has a potential role in a cost-effective


4

INTRODUCTION

A significant amount of fossil water is generated during petroleum production.

This produced water represents the largest volume waste stream in the production

process, and can exceed the total volume of hydrocarbon produced by a factor of ten

(Stephenson 1992). In 1995, the volume of produced water generated in onshore wells

throughout the United States was approximately 17.9 trillion barrels (bbls) (2.8 trillion

m3) (API 2000). Produced water contains an assortment of chemicals including inorganic

salts, metals, and organic substances. Dissolved benzene, toluene, ethylbenzene, and

xylenes (BTEX) are the most abundant hydrocarbons, with BTEX concentrations ranging

from 68 to 600,000 µg/L in various produced waters (Neff and Sauer 1996). Benzene

levels in produced water can surpass the U.S. drinking water standard of 5 µg/L by a

factor of 7000.

Produced water is currently excluded from the Federal Resource Conservation

and Recovery Act (RCRA) Subtitle C regulation of hazardous waste (40 CFR Part

261.4), but is subject to other RCRA sections (40 CFR Parts 260 to 279), the Clean Water

Act (40 CFR Parts 100-129 and 400-503), the Safe Drinking Water Act (40 CFR Parts

141-148), and various state regulations. Surface discharge is governed by the Clean

Water Act and is permitted by the National Pollutant Discharge Elimination System

(NPDES) (40 CFR Part 435). NPDES permits are not issued for onshore discharges of

produced water except for small-volume stripper wells (10 bbls of oil or less per day) or

for discharge water that can be of beneficial use in areas west of the 98th meridian.

NPDES regulations also do not allow coastal discharge of produced water, except for

5

Cook Inlet, Alaska, which is subject to offshore limits. NPDES regulations do allow

offshore produced water discharge with dissolved oil and grease limits of 29 mg/L

(monthly average) and 42 mg/L (daily average). These limits were reduced in 1994 from

previous levels of 48 mg/L (monthly average) and 72 mg/L (daily average) (Otto and

Arnold 1996). Many states are adopting new regulations favoring deep well injection for

produced water disposal (Boysen et al. 2002). With increasing regulations, producers in

situations where injection is not cost-efficient, such as offshore and stripper wells, could

require the development of new treatment options (Lawrence et al. 1995). The changing

regulatory environment has stimulated interest in developing inexpensive techniques for

removing target produced water contaminants from systems of all scales, from isolated,

single-well operations to large oil fields and offshore rigs.

Currently 92% of onshore produced water is disposed via reinjection (API 2000).

However, this is geologically infeasible in some areas and economically infeasible for

many small producers (less than 10 bbl/day). According to the U.S. EPA (2000), the

remaining onshore produced water is disposed of by irrigation (west of the 98th meridian

only) (4%), evaporation/percolation pits (2%), treatment and discharge (1%), and

application to roads (<1%). For offshore producers, discharge to the ocean is far more

practical and cost-effective than reinjection. Current treatment methods (primarily

oil/water separation, hydrocyclones, and gas flotation) focus on separation of oil and

grease from water and are not effective on dissolved organic components including

BTEX.

These dissolved organic compounds occur in produced water at levels that are

dangerous to the environment when discharged, and can reach levels that are thousands

6

of times higher than U.S. drinking water standards. Benzene is just one example of a

known carcinogen found at high concentrations in produced water. Lawrence et al.

(1995) indicated that future regulations will likely require additional removal of dissolved

organic compounds before discharge. Treatment methods for the removal of dissolved

hydrocarbons include chemical clarification, membrane filtration, bubble separation,

photocatalytic oxidation, phytoremediation, and sorption on altered clay minerals,

carbonaceous sorbents, or granular activated carbon (GAC). Tao et al. (1993) reported a

treatment system that utilized chemical clarification, softening, filtration, and reverse

osmosis methods to satisfy California drinking water standards. This method was quite

expensive with high capital and operating costs. Santos and Wiesner (1997) concluded

that membrane filtration (ultrafiltration) results varied with influent water samples and

were unable to report on the overall technical and economic effectiveness. Thoma et al.

(1999) tested bubble separation and found 40% removal of dissolved toluene and

ethylbenzene, but did not report system costs. Bessa et al. (2001) reported on the use of

titanium oxide semiconductors for photocatalytic oxidation of BTEX. While this method

reduces BTEX levels, the expense of the semiconductors would likely inhibit the use of

this technique for smaller producers. Negri and Hinchman (1997) discussed

phytoremediation of produced water, which may prove to be low cost and low

maintenance, but is dependent on local climate and season. Gallup et al. (1996) reported

the commercially available carbonaceous sorbent Ambersorb® exhibits higher sorption

capacity for BTEX than GAC and certain altered clay minerals, and has an operating cost

that is 15-25% that of GAC, although Ambersorb® showed a 1-40% capacity loss after

7

regeneration. No additional information concerning capital and operating costs was

provided.

An additional candidate low-cost sorbent for BTEX removal is surfactant-

modified zeolite (SMZ). SMZ has been studied previously for its ability to sorb

contaminants from various aqueous solutions. Janks and Cadena (1992), Huddleston

(1990), Neel and Bowman (1992), and Bowman et al. (1995) evaluated the ability of

SMZ to sorb organic molecules such as benzene, toluene, and p-xylene. Haggerty and

Bowman (1994) and Bowman et al. (1995) investigated the use of SMZ to sorb divalent

oxyanions such as chromate, sulfate, and selenate. Bowman et al. (2001) have shown the

use of SMZ in an in-situ permeable barrier for remediation of chromate and

perchloroethylene.

Zeolites are natural aluminosilicate minerals that are characterized by cage-like

structures, high surface areas, and high cation-exchange capacities. Large cationic

surfactant molecules, such as hexadecyltrimethylammonium (HDTMA), have a strong

affinity for the zeolite surface and replace positively charged inorganic counterions that

neutralize the negative surface charge of the zeolite. The surfactant molecules impart

hydrophobic properties to the zeolite surface, allowing the zeolite to retain organic

compounds including BTEX (Bowman et al. 2000). Once SMZ is saturated with volatile

organic compounds, it can be regenerated using air sparging (Li and Bowman 2001). The

ability to regenerate SMZ and the low cost of the material (on the order of $460 per

metric ton) increases its economic feasibility in a produced water treatment system.

This study evaluated the use of SMZ as a sorbent for BTEX removal from

produced water. The objectives of this study were to (1) determine the sorptive capacity

8

of SMZ for BTEX, (2) evaluate the long-term effectiveness of SMZ to sorb BTEX over

multiple sorption/regeneration cycles, and (3) build and field test a prototype SMZ


MATERIALS AND METHODS

SMZ Preparation

The zeolite used in this study was a natural clinoptilolite-rich tuff obtained from

the St. Cloud mine near Winston, NM. The mineral composition was 74% clinoptilolite,

5% smectite, 10% quartz/cristobalite, 10% feldspar, and 1% illite. The zeolite had an

external surface area of 15.7 m2/g. The internal cation exchange capacity was 800

meq/kg and the external cation exchange capacity was 90-110 meq/kg (Bowman et al.

2000). The zeolite was crushed and sieved to two different grain sizes: 1.4 to 0.4 mm

(14-40 mesh) for the field test and 0.18 to 0.15 mm (80-100 mesh) for the laboratory

batch and column experiments.

The SMZ used in the laboratory experiments was produced by treating 1000 g of

zeolite with 3000 mL of a 0.10 M HDTMA-Cl (Aldrich, Milwaukee, WI) solution and

shaking for 24 h. The HDTMA-zeolite was rinsed with two 180 mL aliquots of Type I

water (purified with Milli-Q system, Millipore Corp., Bedford, MA) and air-dried. The

final HDTMA loading was 157 mmol HDTMA/kg zeolite. The SMZ for the field test,

bulk produced at the St. Cloud mine and described by Bowman et al. (2001), had an

HDTMA loading of 180 mmol HDTMA/kg zeolite.

9

Produced Water

The site selected for the field test was a produced water treatment facility

operated by Crystal Solutions, LLC. The facility is located near Wamsutter, Wyoming,

where a large natural gas reservoir exists. Produced water from the region is delivered to

the facility by tanker truck, where it is unloaded into an oil/water separation tank.

Overflow from this tank is transferred into a second separation tank. From the second

tank, oil is sent into an oil condensate tank for later processing, while water flows into a

lined separation pond and is then pumped through a series of lined evaporation ponds.

Produced water for use in the laboratory studies was collected from the separation

tanks at this site in December 2002 and stored in sealed 208 L drums. The composition

of this water is shown in Table 1.

BTEX Sorption/Regeneration in Laboratory Columns

Laboratory columns were scaled based upon a proposed field treatment design

using the rapid small-scale column test method, developed for sorption of organic

compounds onto granular activated carbon (Crittenden et al. 1986). The scaling method

is based on the Dispersed Flow Pore and Surface Diffusion Model (DFPSDM) and

incorporates advective flow, axial dispersion and diffusion, liquid phase mass transfer

resistance, local adsorption equilibrium at the exterior surface of the adsorbent, surface

diffusion, pore diffusion, and competitive equilibrium of solutes on the surface

(Crittenden et al. 1986). For perfect similitude between small-scale and large-scale

systems, dimensionless parameters contained in the DFPSDM must be equal in both

systems, and the scaling law is defined as:

10

2

SC SC

LC LC

EBCT dEBCT d

=

(1)

where: SC = small column

LC = large column

EBCT = empty bed contact time (bed volume/volumetric flow rate)

d = particle diameter

Table 2 contains the parameters from the proposed field treatment design that were used

in Eq. 1 to determine the volumetric flow rate in the laboratory column. The EBCT ratio

is 0.0330 and the square of the particle diameter ratio is 0.0332. SMZ particle size in the

laboratory column was chosen to be close to the minimum requirement of a 50-to-1

column diameter-to-particle size ratio to avoid channeling (Crittenden et al. 1991).

Four glass columns (Ace Glass, Vineland, NJ) with a 4 mm radius and 100 mm

length (Table 2) were packed with 80-100 mesh SMZ. Precision made PTFE end-fittings

were designed for use with these columns and provided a leak-tight seal. Four-way

valves (Cole-Parmer, Vernon Hills, IL) were connected to the end-fittings with Luer

fittings. These valves served as sampling ports and could seal the columns shut between

experiments. Once packed, the columns were purged with CO2 for 24 hours to displace

air in the columns. They were then saturated from the bottom with an organic-free

synthetic brine (3110 mg/L HCO3-, 4400 mg/L Cl-, 4020 mg/L Na+) which approximated

the inorganic composition of the produced water (Table 1). The brine was injected with

10-mL gastight syringes (Hamilton, Reno, NV) loaded in a syringe pump (Harvard

Apparatus, Holliston, MA) at an average flow rate of 2.3 * 10-3 L/min (approximately 70

mm/min). These flow conditions were maintained for the duration of the experiments.

11

The columns were assumed to be at steady state when no gas bubbles were visible and

the water-filled column weights remained constant.

A 2 pore-volume (PV) slug of tritiated water tracer (tritium) was injected into

each column to determine the flow velocity and column dispersion coefficient. Effluent

samples were collected every 0.2 PV in 7 mL vials. One-half milliliter of effluent

solution was combined with 4.5 mL of scintillation cocktail solution (ICN Biomedicals,

Inc., Irvine, CA) for analysis with an LS6500 liquid scintillation counter (Beckman

Coulter, Inc., Fullerton, CA).

Produced water for the column experiments was transferred to a collapsible 30 L

Tedlar® Gas Sampling Bag (Alltech Associates, Inc., Deerfield, IL) with a barbed on/off

valve for injection into the columns. The water in the bag was spiked with additional

ethylbenzene and o-xylene (Aldrich, Milwaukee, WI) to yield concentrations of

approximately 15 mg/L, similar to the benzene concentration. The produced water was

continuously injected into the columns until an air-sparging cycle was begun (see below).

To remove iron oxide precipitates from the influent water, 0.45 µm and 0.2 µm nylon

syringe-tip filters (Supelco, Bellefonte, PA) were added in series to the influent tubing

just upstream of the columns. Using the four-way valves, influent and effluent samples

were collected in 10-mL gastight syringes and sealed in 10-mL glass headspace vials

with Teflon-faced butyl septa (Supelco) for subsequent analysis via gas chromatography.

The columns were sampled at 3 PV intervals for the first 20 PV of effluent, 15 PV

intervals for the next 60 PV of effluent, and 50 PV intervals for the remaining effluent.

Flow was terminated when the effluent BTEX concentrations were approximately equal

to influent concentrations (after 450-500 PV).

12

The spent SMZ was regenerated by air-sparging. A compressed air tank and 65-

mm single-float flow controller (Cole-Parmer) were attached to the effluent end of the

columns, reversing the flow direction from the water injection stage. A soap film

flowmeter (Hewlett-Packard, Palo Alto, CA) was attached to the exhaust end. No water

was removed during gravity drainage prior to air-sparging, but most retained water was

removed during the first minute of sparging. The compressed air tank regulator was set

to 30 psi and the flow controller was used to control air flow rate through the columns.

Flow rate was set at 20 mL/min (6 PV/min). Using a 1.0-mL gastight syringe, samples

were collected by withdrawing 0.2 mL from the effluent gas stream and analyzed

immediately by direct injection into the gas chromatograph. Air-sparging continued until

the concentration of each BTEX compound in the effluent gas stream was reduced to 2%

or less of its initial concentration observed during regeneration (approximately 3500 PV

of air).

The regenerated SMZ was again saturated with produced water under the same

conditions as the original saturation, except the columns were not purged with CO2 or

leached with organic-free brine prior to produced water injection. This cycle of produced

water injection/regeneration was repeated for a total of ten repetitions in two duplicate

columns (columns 10A and 10B), while the injection/regeneration cycle was repeated for

a total of five repetitions in two other duplicate columns (columns 5A and 5B). Columns

5A and 5B were operated simultaneously with columns 10A and 10B. Influent and

effluent samples were not collected for columns 5A and 5B, which were used for batch

sorption studies (see below).

13

Sorption Characteristics of Virgin and Regenerated SMZ

Sorption isotherms were prepared using virgin SMZ (no exposure to produced

water), SMZ from columns 5A/5B (SMZ from both columns was combined), and SMZ

from columns 10A/10B (combined). Batch experiments were performed using produced

water. In order to achieve desired initial BTEX concentrations, the produced water was

placed in uncovered beakers for several hours to allow BTEX volatilization, then spiked

with the desired levels of BTEX. Initial concentrations were 3, 6, 9, 12, and 15 mg/L for

benzene, ethylbenzene, p-&m-xylene combined, and o-xylene. Initial concentrations of

toluene were 6, 12, 18, 24, and 30 mg/L. These values were chosen so that the maximum

concentration of each compound was similar to the influent concentration during the

column experiments. Three milliliters of produced water and 0.75 g of SMZ were

combined in 10-mL headspace vials (in duplicate) and shaken for 24 hours at 25ºC,

conditions which have been previously shown sufficient to attain sorption equilibrium

(Neel and Bowman 1992). Each sample was centrifuged at 900 g× for 20 min, and 1 mL

of the supernatant transferred to a 10-ml headspace vial containing 2 mL Type I water for

gas chromatography analysis. To monitor volatilization losses, two sets of duplicate

blank samples containing produced water at each initial BTEX concentration but no SMZ

were prepared, shaken, and centrifuged. One set of blank samples was analyzed without

transferring the water to a separate vial, and the other set of blank samples was analyzed

after transferring 1 mL of water to a separate vial containing 2 mL Type I water,

following the same procedure as the samples containing SMZ. The two sets of blank

samples allowed determination of volatilization losses during the shaking/centrifugation

processes, and during the transfer of supernatant to a vial for analysis.

14

Field Test of a Prototype SMZ Treatment System

The field treatment system consisted of a fiberglass column designed for use in

ion exchange systems with SMZ substituted for the ion exchange resin. The column

design dispersed the influent stream at the top of the SMZ and collected the effluent via a

perforated plate and tube at the bottom. The column dimensions are given in Table 2.

The system was filled to the top with 87.1 kg of 14-40 mesh SMZ.

The field column was connected to the second separation tank at the Crystal

Solutions facility on a 102-mm diameter valve located about 610 mm from the bottom of

the tank. Flow through the SMZ system was driven by approximately 4.5 m of produced

water head in the tank. A flowmeter was installed at the influent end of the column, and

sampling valves were installed at the influent and effluent ends.

Influent and effluent water samples were collected using 10-mL gastight syringes

and stored in 10-mL glass headspace vials sealed with Teflon-faced butyl septa for later

analysis via gas chromatography. A portable photoionization detector (MiniRAE 2000

PID, RAE Systems, Sunnyvale, CA) was used to estimate total concentrations of volatiles

in water and air during produced water treatment and SMZ regeneration. Air samples

were collected during regeneration by affixing Tygon® tubing to the effluent end of the

column and filling 10-mL glass headspace vials with the effluent gas stream until all the

original air in the vial had been displaced. Each vial was quickly closed and sealed with

a Teflon-faced butyl septum.

Produced water was passed through the SMZ system for about 46 hours. The

flow rate began at 85 L/hr (1.6 PV/hr), increased to 108 L/hr (2.1 PV/hr), then dropped to

15

66 L/hr (1.3 PV/hr) at the end of the run. This drop in flow rate was caused by clogging

of the SMZ pores inside the column by particles in the unfiltered water.

Regeneration was performed in the field by attaching a portable air compressor to

the influent port on the column. Air-sparging was performed for 8.5 hours at air flow

rates between 85 and 100 L/min (1.6 to 1.9 PV/min). Following regeneration, another

sorption cycle was performed by passing produced water through the system for an

additional 47 hours. The flow rate ranged from 91 L/hr (1.7 PV/hr) at the beginning of

the run to 62 L/hr (1.2 PV/hr) at the end.

Analytical Methods

Aqueous BTEX concentrations from the laboratory column and batch

experiments were measured using a Hewlett-Packard (HP) Model 7694 headspace

sampler attached to a HP Model 5890A gas chromatograph (GC) with a 10-m, 0.53-mm

I.D. HP-5 capillary column and flame ionization detector. The carrier gas (He) had a

flow rate of 35 mL/min and the split gas (He) flow rate was 28 mL/min. No makeup gas

was utilized. The analyses were performed isothermally at 55°C, with an injector

temperature of 210°C and detector temperature of 240°C. The GC was calibrated during

each run with five BTEX standards of varying concentrations over a linear response

range from 0.5 mg/L to 40 mg/L. p-xylene and m-xylene were not resolved by this

method and were treated as a single compound. For headspace analysis, a 3-mL aqueous

sample was sealed in a 10-mL headspace vial fitted with a Teflon-faced butyl septum.

The headspace sampler run conditions were as follows: Oven temperature 70°C, loop

temperature 75°C, transfer line temperature 75°C, equilibration time 1.0 min,

16

pressurization time 1.0 min, loop fill time 1.0 min, loop equilibration time 0.5 min,

injection time 0.09 min.

The BTEX concentrations in gas samples from both lab and field air-sparging

were analyzed by direct injection into the HP 5890A GC. Calibration standards in Milli-

Q water were prepared in 10-mL headspace vials fitted with Teflon face butyl septum.

Based on the Henry’s constants and the known aqueous concentration, the BTEX mass

removed from the headspace and injected into the GC was calculated. All GC operating

conditions were the same as above, with the split flow increased to 63 mL/min.

Aqueous BTEX concentrations in samples from the field columns were measured

using a Tekmar 7000 headspace sampler attached to a HP Model 5890 gas

chromatograph with a 30-m, 0.53-mm I.D. Restek capillary column (RTX-624) and

flame ionization detector. The carrier gas (He) had a flow rate of 36 mL/min and

nitrogen was added as a makeup gas. No split flow was utilized. The analyses were

performed with an initial temperature of 40°C for 1 minute, followed by a 20°C/min

ramp to 85°C, and then increased at 0.5°C/min to a final temperature of 90°C held for 1

minute. The injector temperature was 250°C and detector temperature was 275°C. The

GC was calibrated during each run with eleven BTEX standards of varying

concentrations over a linear response range up to 1.5 mg/L of each BTEX compound. p-

xylene and m-xylene were not resolved by this method and were treated as a single

compound. For headspace analysis, a 50-µL sample was diluted with 5 mL of Milli-Q

water and sealed in a 22-mL headspace vial fitted with a Teflon-faced butyl septum. The

headspace sampler run conditions were as follows: Oven temperature 80°C, loop

temperature 170°C, transfer line temperature 170°C, equilibration time 15.0 min, mixing

17

time 10.0 min, pressurization time 1.0 min, pressure equilibration time 0.25 min, loop fill

time 1.0 min, loop equilibration time 0.25 min, injection time 1.0 min.

RESULTS AND DISCUSSION

BTEX Sorption/Regeneration in Laboratory Columns

The tritium BTCs for the columns were well described by the simple 1-

dimensional advection-dispersion equation:

* 2 * *

2

1C C CRp P X X

∂ ∂ ∂= −

∂ ∂ ∂ (2)

where:

0

* CCC

= (3)

vLPD

= (4)

1 dR Kρθ

= +

(5)

vtpL

= (6)

xXL

= (7)

and C is the effluent solute concentration (M/L3), C0 is the influent solute concentration

(M/L3), C* is the dimensionless solute concentration, D is the dispersion coefficient

(L2/T), v is the pore-water velocity (L/T), x is the distance (L), L is the column length (L),

p is dimensionless time (pore volumes), ρ is bulk density (M/L3), θ is volumetric water

18

content, Kd is the linear equilibrium sorption constant (L3/M), P is the Peclet number, and

R is the retardation factor.

Equation 2 was fitted to the observed tritium data using the nonlinear, least-

squares optimization program CXTFIT 2.1 under flux-type boundary conditions (Toride

et al. 1999). The pore-water velocity v was treated as a fixed value and R and D were

fitted. All four columns yielded similar tritium BTCs with symmetrical shapes and R

values in the range 0.955 to 1.13. The BTC for column 10A is shown in Figure 1. A dip

in C* was observed at about 2 PV for all columns, corresponding to the time at which

flow through the columns was interrupted to change the influent from tritiated to non-

tritiated brine. When flow was stopped, a pressure drop throughout the system likely

allowed the tritiated brine in effluent end of the column to mix with lower-tritium brine

residing in the column end-fitting.

Figure 2 shows the results of BTEX breakthrough on virgin SMZ in column 1.

The equilibrium one-dimensional advection-dispersion equation (Eq. 2) did not

adequately fit the observed data, so sorption of BTEX in the column experiments was

analyzed with a bicontinuum model.

The bicontinuum model can be used to describe both physical and chemical

nonequilibrium. Because the tritium BTCs did not exhibit early breakthrough or

significant tailing, physical nonequilibrium was likely not significant and the processes

causing nonequilibrium behavior in the BTEX BTCs are probably related to sorption

nonequilibrium (Brusseau and Rao 1989). The mechanisms behind slow sorption are not

fully understood, but it is often attributed to diffusion control (Pignatello and Xing 1996).

We assume slow sorption involves diffusion of BTEX within the hydrophobic region

19

created by the surfactant molecules on the surface of SMZ. Under the first-order mass

transfer model described by Brusseau et al. (1991), sorption occurs in two regions

characterized by either instantaneous or rate-limited sorption:

1 dS FK C= (8)

21 2f r

dS k S k Sdt

= − (9)

where S1 is the sorbed concentration (M/M) in the instantaneous sorption region, S2 is the

sorbed concentration (M/M) in the rate-limited sorption region, F is the fraction of

instantaneous sorption sites, t is time, and kf and kr are forward and reverse first-order rate

constants (1/T), respectively.

The 1-dimensional advective-dispersive transport equation accounting for

kinetically limited sorption and assuming steady-state water flow and a homogeneous

porous medium, leads to the following equations (Brusseau et al. 1991):

2

2

* * * * *( 1) (1 ) (1/ )C C S C CR R Pp p p X X

β β∂ ∂ ∂ ∂ ∂+ − + − = −

∂ ∂ ∂ ∂ ∂ (10)

*(1 ) ( * *)SR C Sp

β ω∂− = −

∂ (11)

where:

2*(1 ) d

SS KF

=−

(12)

1 dF K

R

ρθβ

+ = (13)

2 (1 )k RLvβω −

= (14)

20

S* is the dimensionless sorbed concentration in the rate-limited domain, ω is the

Damkohler number, the ratio of characteristic sorption time to hydrodynamic residence

time.

The solution to Eqs. 10 and 11 requires estimation of four parameters (P, R, ω,

and β). The value of P was determined from the tritium BTCs using Eq. 4. The value for

R was determined from Eq. 5 by estimating Kd directly from the BTEX breakthrough

curves, using the areas between the influent and effluent BTEX concentrations to

determine S (S=S1+S2). The parameter S was then related to Kd by Eq. 8 assuming

equilibrium had been reached and F=1. Benzene and toluene had reached equilibrium

and the actual value of C was used in Eq. 8 for these compounds. For ethylbenzene and

the xylenes, which had not reached equilibrium by the end of each sorption cycle, we

used the average of the final values of C and C0 as a measure of C. The other two

sorption parameters, ω and β, were optimized by fitting Eq. 10 to the experimental data

with CXTFIT 2.1.

As shown in Figure 2, benzene breakthrough occurs first because of its high

solubility in water and low octanol-water partition coefficient Kow (Table 1), while the

other compounds elute in order of increasing Kow. The BTCs of ethylbenzene and

xylenes are similar due to their similar Kow values (Table 1). Benzene begins to elute

from the column after approximately 8 PV of produced water have been injected, while

the xylenes and ethylbenzene do not rise above initial effluent concentrations until after

50 PV of water have been injected.

21

Reproducibility between the BTCs for replicate columns was good. Figures 3a

and 3b show the BTCs for benzene and p-&m-xylene during the first and fifth sorption

cycles in duplicate columns.

Figures 4a and 4b show the breakthrough of benzene and p-&m-xylene, respec-

tively, in Column 10A over 10 sorption/regeneration cycles. The BTCs for each BTEX

compound changed little over these 10 cycles, indicating little reduction in the sorption

capacity of SMZ upon repeated saturation and air-stripping. In fact, the BTC during the

first injection shows the earliest breakthrough (least sorption and retardation) for each

compound. The removal efficiency may have increased because of the retention of low

volatility components in produced water during regeneration which could create an

additional sorption medium for the partitioning of BTEX (Jaynes and Vance 1996).

During these 10 cycles, approximately 4500 PV of water passed through each column.

With repeated sorption cycles, backpressures increased in each column. This was

investigated after completion of the ten sorption/regeneration cycles by examining virgin

SMZ and SMZ from Columns 10A/10B and 5A/5B with a scanning electron microscope

(SEM). The SEM results showed that the SMZ particles were breaking apart, creating

finer particles which reduced column permeability and increased backpressure. Many

particles from Columns 10A/10B were 10% of the size of the virgin SMZ grains. The

cause of the particle breakdown is not understood and could be either mechanical or

chemical in origin. With no significant reduction in sorption capacity after 10

sorption/regeneration cycles, the breakdown of SMZ particles and subsequent increase in

column backpressure may play the largest role in determining the lifetime of SMZ in a

produced-water treatment system.

22

Table 3 shows the Kd values calculated for each BTEX compound in Columns

10A and 10B. The Kd values determined by the tenth sorption cycle were not considered

because sorption was not completed during this cycle due to high column backpressures.

Using a regression coefficient significance test (Edwards 1984), the Kd values for

benzene and toluene showed no statistically significant trends throughout the first nine

sorption/regeneration cycles, while there was a decreasing trend in Kd for ethylbenzene

and xylenes. The average decrease in Kd for ethylbenzene and the xylenes was

approximately 2.7 L/kg per sorption cycle in Column 10a and 7.2 L/kg per sorption cycle

in Column 10b. T-tests showed that the mean Kd values for each BTEX compound were

statistically equivalent (95% confidence level) between replicate columns 10A and 10B

throughout the first nine sorption cycles.

The mass of BTEX removed from Column 10A by air-sparging after the first

injection of BTEX is shown in Figure 5. The compounds with the highest aqueous

solubility were the most readily removed. Air-sparging effectively stripped

approximately 100% of the benzene from the columns, 90% of the toluene, and 75% of

the lowest solubility BTEX compounds (only p-&m-xylene shown). Air-sparging results

throughout the remaining nine regeneration cycles showed similar patterns as in Figure 5.

Duplicate columns showed comparable sparging results.

Sorption Characteristics of Virgin and Regenerated SMZ

The batch sorption study performed on virgin SMZ (no prior BTEX exposure),

SMZ that had experienced 5 sorption/regeneration cycles, and SMZ that had undergone

10 sorption/regeneration cycles confirmed that the SMZ had not lost any significant

23

sorption capacity for BTEX after 5 and 10 cycles. Sorption data for each SMZ batch

were well-described by the linear sorption model (Eq. 8 with F = 1), with all R2 ≥ 0.77

and most R2 ≥ 0.92. The Kds for each BTEX compound on virgin and exposed SMZ

were statistically indistinguishable. The means and standard deviations of Kd for each

BTEX compound are shown in Table 3. These batch sorption results are consistent with

our column results showing SMZ does not lose sorption capacity for BTEX over 10

sorption/regeneration cycles (> 4500 PV of exposure to produced water). Table 3 shows

that Kd values determined from batch experiments were, however, significantly lower

than Kd values determined from column experiments. Results from other studies have

shown disagreement in Kd between batch and column experiments. Several different

reasons for the differences have been hypothesized, including immobile water in the

column (MacIntyre et al. 1991), failure to reach sorption equilibrium in batch

experiments (Streck et al. 1995), destruction of particles while shaking (Schweich et al.

1983), reduction in column particle spacing (Celorie et al. 1989), and inappropriate

application of an equilibrium sorption model (Altfelder et al. 2001). The reasons for the

discrepancies between batch and column Kds in our experiments are unclear.

Field Test of a Prototype SMZ Treatment System

The breakthrough of benzene and toluene on virgin SMZ in the field column is

shown in Figure 6. The effluent concentration of ethylbenzene and xylenes remained

near zero after 80 PV (not shown in Figure 6). Figure 6 includes a comparison of the

BTC for benzene and toluene on virgin SMZ in the laboratory columns. The field

column exhibited later breakthrough and stronger retention of BTEX than the laboratory

24

column. Although the two systems are scaled, the likely reason for this is that the 14-40

mesh SMZ used in the field column has a higher surfactant loading (180 mmol

HDTMA/kg zeolite) than the 80-100 mesh SMZ used in the laboratory columns (157

mmol HDTMA/kg zeolite).

Figure 7 shows the BTCs for benzene and toluene on virgin and regenerated SMZ

in the field column. The effluent concentrations for ethylbenzene and the xylenes were

again very low and are not shown in Figure 7. The initial effluent concentrations of

toluene (and ethylbenzene and xylenes) were above zero, which was higher than during

any stage of the initial sorption experiment. These relatively high effluent concentrations

were likely due to incomplete regeneration of the SMZ. During regeneration, air flow

was in the same direction as water flow in the column, pushing the BTEX toward the

effluent end of the column. The compounds with higher Kow were likely not completely

removed during sparging, but instead were concentrated toward the effluent end of the

column. When produced water was reintroduced to the column for the second sorption

cycle, these higher concentrations eluted. By reversing flow during air-sparging as in the

laboratory columns, this problem could be eliminated as BTEX would be concentrated

toward the influent end of the column if sparging was incomplete. Aside from the high

concentration of toluene initially, Figure 7 shows that the regenerated SMZ was even

more effective at BTEX removal than the virgin SMZ, similar to the trend observed in the

laboratory columns.

25

CONCLUSIONS

Surfactant-modified zeolite successfully removed BTEX from produced water

with components eluting from columns in order of decreasing water solubility/increasing

Kow. The SMZ was regenerated by air-sparging and continued to remove BTEX from

produced water. After 10 cycles of sorption/regeneration with a total of > 4500 pore

volumes of water treated, SMZ showed no significant reduction in sorption capacity. In

fact, the earliest breakthrough (least sorption) of BTEX compounds was observed on

virgin zeolite. Batch experiments provided further evidence that surfactant-modified

zeolite did not lose any significant capacity for BTEX sorption after 10

sorption/regeneration cycles. However, as the column experiments progressed, the SMZ

particles were breaking down into finer grained particles which reduced the column

permeability and increased the backpressure.

Field-scale tests supported laboratory column test data, showing even greater

sorption of BTEX from produced water than was observed in the laboratory columns.

The results of this study along with the low cost of SMZ suggest that surfactant-modified

zeolite may have use in cost-effective produced-water treatment systems.

ACKNOWLEDGEMENTS

This work was funded by the U.S. Department of Energy (DE-AC26-99BC15221). We

thank Mr. John Boysen of B.C. Technologies (Laramie, WY) for the use of their

facilities. Guifang Tan of the University of Texas-Austin prepared the SMZ, performed

26

the gas chromatography analyses of the field-test samples, and provided assistance with

the field test. Sarah Loughney of New Mexico Tech assisted with laboratory column

experiments. Jim Smith of Los Alamos National Laboratory assisted with SEM analysis.

Alana Fuierer of New Mexico Tech aided with the setup of the laboratory column

system.

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Janks, J.S., and Cadena, F. (1992). "Investigations into the use of modified zeolites for removing benzene, toluene, and xylene from saline produced water." Produced Water, J.P. Ray and F.R. Engelhart, eds., Plenum Press, New York, 473-487.

Jaynes, W. F., and Vance, G. F. (1996). "BTEX sorption by organo-clays: cosorptive

enhancement and equivalence of interlayer complexes." Soil Sci. Soc. Am. J., 60(6), 1742-1749.

Lawrence, A. W., Miller, J.A., Miller, D.L., and Hayes, T.D. (1995). "Regional

assessment of produced water treatment and disposal practices and research needs." Proc., SPE/EPA Exploration and Production Environmental Conference, Society of Petroleum Engineers, Houston, Texas, 373-392.

Li, Z., and Bowman, R. S. (2001). "Regeneration of surfactant-modified zeolite after

saturation with chromate and perchloroethylene." Wat. Res., 35(1), 322-326. MacIntyre, W. G., Stauffer, T. B., and Antworth, C. P. (1991) "A comparison of sorption

coefficients determined by batch, column, and box methods on a low organic carbon aquifer material." Ground Water, 29(6) 908-913.

Mackay, D., Shiu, W. Y., and Ma, K. C. (1992). “Illustrated handbook of physical-

chemical properties and environmental fate for organic chemicals,” Lewis Publishers, Chelsea, MI.

Neel, D., and Bowman, R. S. (1992). "Sorption of organics to surface-altered zeolites."

Proc., 36th Annual New Mexico Water Conference, New Mexico Water Resources Research Institute, Las Cruces, NM, 57-61.

Neff, J. M., and Sauer, Jr, T.C. (1996). "Aromatic hydrocarbons in produced water."

Produced Water 2: Environmental Issues and Mitigation Technologies, M. Reed and S. Johnsen, eds., Plenum Press, New York, 163-175.

Negri, M. C., and Hinchman, R. C. (1997). “Biotreatment of produced waters for volume

reduction and contaminant removal.” Proc., 4th Annual International Petroleum Environmental Conference: Issues and Solutions, Production and Refining. Integrated Petroleum Environmental Consortium, San Antonio, Texas.

Otto, G. H., and Arnold, K. E. (1996). "U.S. produced water discharge regulations have

tough limits." Oil and Gas J., 94(29) 54-61. Pignatello, J. J., and Xing, B. (1996). "Mechanisms of slow sorption of organic chemicals

to natural particles." Environ. Sci. Technol., 30(1), 1-11. Santos, S. M., and Wiesner, M. R. (1997). “Ultrafiltration of water generated in oil and

gas production.” Water Environ. Res., 69(6) 1120-1127.

29

Schweich, D., Sardin, M., and Guedent, J. P. (1983). "Measurement of a cation exchange isotherm from elution curves obtained in a soil column: Preliminary results." Soil Sci. Soc. Am. J., 47(1) 32-37.

Stephenson, M. T. (1992). "A survey of produced water studies." Produced Water, J. P.

Ray and F. R. Engelhart, eds., Plenum Press, New York, 1-11. Streck, T., Poletika, N. N., Jury, W. A., and Farmer, W. J. (1995). "Description of

simazine transport with rate-limited, two-stage, linear and nonlinear sorption." Water Resour. Res., 31(4) 811-822.

Tao, F. T., Curtice, S., Hobbs, R. D., Sides, J. L., Wieser, J. D., Dyke, C. A., Tuohey, D.,

and Pilger, P. F. (1993). “Reverse osmosis process successfully converts oil field brine into freshwater.” Oil and Gas J., 91(38) 88-91.

Thoma, G. J., Bowen, M. L., and Hollensworth, D. (1999). “Dissolved air

precipitation/solvent sublation for oil-field produced water treatment.” Separation and Purification Tech., 16(2) 101-107.

Toride, N., Leij, F.J., and van Genuchten, M.T. (1999). "The CXTFIT code for

estimating transport parameters from laboratory or field tracer experiments, version 2.1." Research Report No. 137, U.S. Salinity Laboratory, USDA, ARS, Riverside, CA.

U.S. EPA. (2000). "Profile of the oil and gas extraction industry." EPA/310-R-99-006,

Washington, DC.

APPENDIX II. NOTATION

The following symbols are used in this paper:

C = liquid-phase concentration (M/L3);

C* = dimensionless solute concentration;

D = dispersion coefficient (L2/T);

d = particle diameter (mm);

F = fraction of instantaneous sorption sites (dimensionless);

Kd = equilibrium sorption constant (L3/M);

30

Kow = octanol-water partition coefficient (dimensionless);

k = first-order rate constant (dimensionless);

L = column length (L);

P = Peclet number (dimensionless);

p = dimensionless time (pore volumes);

R = retardation factor (dimensionless);

S = sorbed concentration (M/M);

S* = dimensionless sorbed concentration in rate-limited sorption region;

t = time (T);

v = pore-water velocity (L/T);

x = distance (L);

θ = volumetric water content (dimensionless);

ρ = bulk density (M/L3);

ω = Damkohler number (dimensionless);

SUBSCRIPTS

f = forward;

r = reverse;

0 = influent concentration;

1 = instantaneous sorption region;

2 = rate-limited sorption region;

31

Table 1. Analysis of produced water used in laboratory experiments.

Analysis1 Amount

(mg/L)

log Kow2 Solubility

(mg/L) 25ºC2

Benzene 15.8 2.13 1850

Toluene 36.7 2.69 470

Ethylbenzene 1.4 3.15 140

p-xylene & m-xylene 6.4 3.15, 3.20 200, 173

o-xylene 3.4 3.15 204

Cl- 4,400

HCO3- 3,120

F- 57

Br- 22

SO4- 13

Na+ 4,100

K+ 44

Ca2+ 30

Mg2+ 6.4

Total Dissolved Solids 11,792

Total Organic Carbon 1,000

1 Inorganic anions determined by ion chromatography. Inorganic cations determined by flame atomic absorption. TDS determined by addition of anions and cations. TOC determined by combustion. BTEX compounds determined as described in Methods section. 2 Mackay, D., et al. (1992).

32

Table 2. Dimensions and operating parameters for field and laboratory columns.

Field Column Laboratory Column

Column radius (mm) 178 4.0

Column length (mm) 1220 100

Bed volume (L) 1021 5.03 * 10-3

Ave. SMZ particle size (mm) 0.90 0.164

Volumetric flow rate (L/min) 1.67 2.92 * 10-3

EBCT (min) 52.3 1.74

1 Bed volume (total volume of grains and voids) is less than volume calculated from column dimensions because of internal column plumbing.

33

Table 3. Mean Kd values determined by laboratory column and batch experiments. Standard

deviations are shown in parentheses. “n” indicates the number of measurements for each mean.

Compound Mean Column Kd (L/kg) (n=18) Mean Batch Kd (L/kg) (n=6)

Benzene 18.3 (4.70) 6.71 (0.57)

Toluene 37.5 (5.27) 15.6 (1.32)

Ethylbenzene 88.0 (10.9) 33.5 (2.87)

p-&m-xylene 95.0 (11.3) 36.5 (2.61)

o-xylene 87.7 (11.5) 39.4 (3.37)

34

FIGURE CAPTIONS

Figure 1. Observed and fitted (Eq. 2) breakthrough curves for tritiated water in

Column 10A.

Figure 2. Observed and fitted BTEX breakthrough curves on virgin SMZ (Column

10A). The lines were based on the best fit of eq. 10 to the observed data,

as described in the text.

Figure 3. BTCs of benzene and p-&m-xylene in Columns 10A and 10B for (a)

virgin SMZ and (b) during the fifth sorption cycle.

Figure 4. (a) Benzene BTCs for Column 10A over 10 sorption/regeneration cycles

and (b) p-&m-xylene BTCs for Column 10A over 10

sorption/regeneration cycles.

Figure 5. Cumulative masses of benzene, toluene, and p-&m-xylene removed

relative to masses sorbed during first regeneration in Column 10A.

Figure 6. Comparison of benzene and toluene BTC for virgin SMZ in lab column

10A and field column.

Figure 7. Benzene and toluene breakthrough on virgin and regenerated SMZ in field

column.

35

0 2 4 6PORE VOLUMES OF WATER

0

0.2

0.4

0.6

0.8

1C

/C0

Figure 1. Observed and fitted (Eq. 2) breakthrough curves for tritiated water in Column 10A.

36

0 100 200 300 400 500PORE VOLUMES OF PRODUCED WATER

0

0.2

0.4

0.6

0.8

1C

/C0

Benzene

Toluene

Ethylbenzene

o-xylene

p-&m-xylene

Figure 2. Observed and fitted BTEX breakthrough curves on virgin SMZ (Column 10A). The lines

were based on the best fit of eq. 10 to the observed data, as described in the text.

37


0

0.2

0.4

0.6

0.8

1C

/C0

Column 10A BenzeneColumn 10B BenzeneColumn 10A p-&m-xyleneColumn 10B p-&m-xylene

(a) Virgin SMZ


0

0.2

0.4

0.6

0.8

1

C/C

0

Column 10A BenzeneColumn 10B BenzeneColumn 10A p-&m-xyleneColumn 10B p-&m-xylene

(b) 5th sorption cycle

Figure 3. BTCs of benzene and p-&m-xylene in Columns 10A and 10B for (a) virgin SMZ and (b)

during the fifth sorption cycle in columns 10A and 10B.

38


0

0.2

0.4

0.6

0.8

1C

/C0

BTC 1BTC 2BTC 3BTC 4BTC 5BTC 6BTC 7BTC 8BTC 9BTC 10

(a) benzene


0

0.2

0.4

0.6

0.8

1

C/C

0


(b) p-&m-xylene

Figure 4. (a) Benzene BTCs for Column 10A over 10 sorption/regeneration cycles and (b) p-&m-

xylene BTCs for Column 10A over 10 sorption/regeneration cycles.

39

0 500 1000 1500 2000 2500 3000PORE VOLUMES OF AIR

0

0.2

0.4

0.6

0.8

1

REL

ATI

VE M

ASS

REM

OVE

D

Benzene

Toluene

p-&m-xylene

Figure 5. Cumulative masses of benzene, toluene, and p-&m-xylene removed relative to masses

sorbed during first regeneration in Column 10A.

40

0 10 20 30 40 50 60 70 80 90 100PORE VOLUMES OF PRODUCED WATER

0

0.2

0.4

0.6

0.8

1

C/C

0

Benzene lab Column 10A

Benzene field column

Toluene lab Column 10A

Toluene field column

Figure 6. Comparison of benzene and toluene BTC for virgin SMZ in lab column 10A and field

column.

41


0

0.2

0.4

0.6

0.8

1

C/C

0

Benzene regenerated SMZ

Benzenevirgin SMZ

Toluenevirgin SMZ

TolueneregeneratedSMZ

Figure 7. Benzene and toluene breakthrough on virgin and regenerated SMZ in field column.

42

INTRODUCTION TO APPENDICES

The following appendices provide descriptions of preliminary and unreported

studies, further information on methods used, and the experimental data collected

throughout the thesis project.

Appendix A contains a description of the preliminary laboratory column

experiments and results.

Appendix B contains the tabulated results of the tritium tracer tests in the

laboratory columns. This includes the tracer tests described in the manuscript and also

unreported tracer tests performed following the completion of the sorption/regeneration

cycle tests. A discussion of SMZ loss from the columns is provided. The discussion

continues with the results of the investigation of the causes of high backpressures in the

column during the late sorption cycles by comparison of virgin SMZ, SMZ from

Columns 5A/5B, and SMZ from Columns 10A/10B using a scanning electron

microscope.

Appendix C provides the BTC data for the 10 sorption/regeneration cycles for

Columns 10A and 10B.

Appendix D presents the data from the batch experiments.

Appendix E contains a more detailed explanation of the field treatment system

and the full results from these experiments.

Appendix F presents information about organic compounds present in this

produced water in addition to BTEX. A discussion of known semi-volatiles in the

produced water is provided, along with a discussion of potential unquantified compounds

43

and how the presence of other organic compounds may affect the use of SMZ in a

treatment system.

Appendix G contains a discussion outlining applicable produced waters for use in

an SMZ treatment system.

44

APPENDIX A. PRELIMINARY LAB COLUMN DISCUSSION AND DATA

In the early stages of this project, a study was conducted using a column not

discussed in the preceding manuscript. The column dimensions were scaled from a

proposed field treatment design using the rapid small-scale column test method as

described in the manuscript. The proposed field setup and scaling parameters are

described by Tan (2002). The field system was then re-designed after experiments with

this column had been performed, leading to re-scaling for the columns described in

Chapter 2. The column (Ace Glass) had a 0.8 cm diameter, 25 cm length, and was

packed with 80-100 mesh SMZ. The end-fittings and sampling port fixtures were

identical to the setup described in the manuscript, although no syringe-tip filters were

required as no iron oxide precipitates were present in the influent water. Once packed,

the column was purged with CO2 gas and saturated from the bottom with purified water

(Type I). The water was injected using the same syringe pump setup described in the

manuscript. No tritium tracer test was completed for this column, and no duplicate

columns were operated. The influent BTEX solution was prepared by combining BTEX

and Type I water in a collapsible 10-L (12” x 19”) Tedlar® Gas Sampling Bag (Alltech)

with a barbed on/off valve. The BTEX concentration was 16 mg/L for each of the six

compounds. The BTEX solution was injected into the saturated column at a flow rate of

1.19 cm/min. Influent and effluent samples were collected in the same manner as

described previously.

Once the effluent BTEX concentrations were approximately equal to influent

concentrations, flow was terminated and the column was then regenerated by air-sparging

45

in the same manner as the method described in previously. In this study, however, the air

flowrate was 2.3 mL/min. Following regeneration, a second sorption/regeneration cycle

was completed with this column. The results of these two sorption/regeneration cycles

follow. Appendix Table A-1 contains the BTC data on virgin SMZ in the preliminary

column. Appendix Tables A-2 through A-6 contain the air-sparging data for this column.

The BTC data on regenerated SMZ in the preliminary lab column are presented in

Appendix Table A-7.

Results from these column experiments are further discussed by Ranck et al.

(2002).

APPENDIX A REFERENCE

Ranck, J.M., J.L. Weeber, G. Tan, E.J. Sullivan, L.E. Katz, and R.S. Bowman. (2002)

“Removal of BTEX from produced waters using surfactant-modified zeolite.”

Proc., 9th Annu. International Petroleum Environmental Conference, Integrated

Petroleum Environmental Consortium, Albuquerque, NM.

46

Appendix Table A-1. BTEX BTC data on virgin SMZ in preliminary lab column.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m- xylene C/Co

o-xylene C/Co

1 0.0 0.000 0.000 0.000 0.000 0.000 2 3.1 0.000 0.001 0.001 0.002 0.000 3 5.1 0.000 0.001 0.001 0.001 0.000 4 6.8 0.007 0.001 0.001 0.001 0.000 5 8.6 0.161 0.001 0.001 0.001 0.000 6 10.4 0.578 0.001 0.001 0.001 0.000 7 12.8 0.763 0.001 0.001 0.001 0.000 8 14.3 0.744 0.000 0.001 0.001 0.000 9 16.1 0.858 0.003 0.001 0.000 0.000 10 18.0 0.583 0.017 0.001 0.001 0.000 11 19.9 0.876 0.060 0.001 0.001 0.000 12 21.7 0.850 0.129 0.001 0.001 0.000 13 23.7 0.837 0.206 0.001 0.001 0.000 14 25.5 1.281 0.465 0.001 0.001 0.000 15 27.4 0.948 0.421 0.001 0.001 0.000 16 29.4 0.961 0.507 0.001 0.001 0.000 17 31.3 0.959 0.568 0.001 0.001 0.000 18 33.3 0.958 0.617 0.001 0.001 0.000 19 35.2 0.957 0.647 0.001 0.001 0.000 20 38.6 1.006 0.725 0.002 0.001 0.000 21 40.7 0.907 0.659 0.002 0.001 0.002 22 42.7 1.033 0.783 0.003 0.001 0.005 23 44.7 0.795 0.601 0.001 0.001 0.007 24 46.6 1.081 0.851 0.016 0.003 0.019 25 48.7 1.002 0.772 0.022 0.004 0.026 26 51.3 1.094 0.867 0.043 0.009 0.048 27 54.5 0.969 0.745 0.053 0.013 0.061 28 57.9 0.998 0.794 0.088 0.027 0.098 29 60.5 1.006 0.814 0.113 0.070 0.125 30 63.1 0.889 0.670 0.114 0.045 0.125 31 65.9 0.897 0.691 0.136 0.061 0.149 32 67.2 0.872 0.665 0.137 0.063 0.153 33 72.5 0.962 0.800 0.215 0.115 0.229 34 75.8 no data no data no data no data no data 35 79.8 no data no data no data no data no data 36 83.5 no data no data no data no data no data 37 87.5 no data no data no data no data no data 38 91.3 no data no data no data no data no data 39 95.5 no data no data no data no data no data

47

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m- xylene C/Co

o-xylene C/Co

40 100.2 no data no data no data no data no data 41 103.7 no data no data no data no data no data 42 110.9 no data no data no data no data no data 43 115.4 no data no data no data no data no data 44 118.2 no data no data no data no data no data 45 121.5 no data no data no data no data no data 46 125.0 no data no data no data no data no data 47 132.5 no data no data no data no data no data 48 138.4 0.965 0.886 0.609 0.551 0.607 49 144.6 0.873 0.767 0.553 0.495 0.545 50 149.0 0.937 0.850 0.628 0.580 0.636 51 155.3 0.951 0.863 0.663 0.618 0.665 52 162.1 0.891 0.807 0.630 0.585 0.632 53 173.8 0.877 0.810 0.636 0.599 0.630 54 187.2 0.958 0.940 0.800 0.774 0.772 55 196.2 1.023 1.021 0.904 0.867 0.877 56 199.2 0.901 0.867 0.757 0.736 0.736 57 204.7 0.864 0.798 0.695 0.686 0.694 58 210.5 0.877 0.845 0.760 0.738 0.740 59 226.3 0.896 0.886 0.843 0.821 0.822 60 231.2 0.956 0.925 0.901 0.892 0.876 61 239.1 1.038 1.035 1.016 1.038 0.990 62 244.8 0.981 0.955 0.959 0.968 0.944 63 248.3 0.969 0.955 0.968 0.981 0.946 64 252.6 1.170 1.273 1.327 1.365 1.293 65 265.9 1.028 1.087 1.138 1.180 1.109 66 276.4 0.987 1.023 1.069 1.122 1.060 67 281.0 0.928 0.900 0.902 0.937 0.877 68 284.3 0.985 1.010 1.058 1.104 1.065 69 294.6 0.933 0.923 0.962 0.986 0.936 70 308.9 1.167 1.182 1.304 1.333 1.238 71 313.2 0.916 0.895 0.995 1.014 0.957

48

Appendix Table A-2. Benzene removal data

Sample

Pore Volumes

Concentration(mg/L)

Total Mass Removed (mg)

Start 0.0 0.000 0.000 1 1.5 2.322 0.025 2 9.9 1.977 0.148 3 18.4 1.540 0.244 4 27.7 2.280 0.401 5 35.5 1.840 0.506 6 46.1 2.550 0.705 7 53.7 1.610 0.795 8 63.1 1.370 0.890 9 72.0 1.297 0.975 10 81.6 1.364 1.071 11 90.2 1.681 1.178 12 99.0 1.351 1.265 13 108.4 1.198 1.349 14 120.9 0.542 1.398 15 129.2 0.443 1.425 16 138.0 0.328 1.447 17 147.4 0.370 1.472 18 156.8 0.259 1.490 19 166.2 0.180 1.503 20 175.8 0.135 1.512 21 185.2 0.102 1.519 22 194.7 0.101 1.526 23 205.7 0.078 1.533 24 216.8 0.058 1.537 25 226.4 0.045 1.540 26 252.2 0.051 1.550 27 261.8 0.041 1.553 28 272.5 0.037 1.556 29 281.2 0.032 1.558 30 292.0 0.023 1.560 31 300.7 0.018 1.561 32 310.4 0.023 1.563 33 320.1 0.014 1.564 34 329.9 0.022 1.565

49

Sample

Pore Volumes

Concentration(mg/L)


35 339.6 0.011 1.566 36 349.3 0.009 1.567 37 358.9 0.008 1.567 38 371.7 0.008 1.568 39 384.5 0.007 1.569 40 396.1 0.005 1.569 41 410.2 0.006 1.570 42 459.2 0.002 1.570 43 476.1 0.005 1.571 44 490.8 0.003 1.571 45 503.7 0.003 1.572 46 518.6 0.000 1.572 47 533.1 0.000 1.572 48 547.3 0.000 1.572 49 561.6 0.000 1.572 50 591.1 0.000 1.572 51 605.8 0.000 1.572 52 635.6 0.000 1.572 53 665.3 0.000 1.572 54 692.6 0.000 1.572 55 721.9 0.000 1.572 56 889.7 0.000 1.572 57 1231.2 0.000 1.572 59 1252.9 0.000 1.572 60 1508.6 0.000 1.572 61 1609.8 0.000 1.572 62 2047.8 0.000 1.572 63 2270.6 0.000 1.572

50

Appendix Table A-3. Toluene removal data

Sample

Pore Volumes

Concentration(mg/L)


Start 0.0 0.000 0.000 1 1.5 3.066 0.033 2 9.9 2.685 0.200 3 18.4 2.094 0.330 4 27.7 3.154 0.548 5 35.5 2.494 0.690 6 46.1 3.476 0.962 7 53.7 2.260 1.088 8 63.1 1.991 1.225 9 72.0 1.930 1.353 10 81.6 2.130 1.502 11 90.2 2.856 1.684 12 99.0 2.683 1.857 13 108.4 2.933 2.061 14 120.9 1.909 2.236 15 129.2 2.026 2.360 16 138.0 1.960 2.488 17 147.4 2.861 2.684 18 156.8 2.489 2.856 19 166.2 2.331 3.017 20 175.8 2.203 3.173 21 185.2 2.028 3.314 22 194.7 2.423 3.483 23 205.7 2.279 3.668 24 216.8 2.023 3.832 25 226.4 1.896 3.967 26 252.2 1.919 4.331 27 261.8 1.547 4.441 28 272.5 1.358 4.548 29 281.2 1.159 4.622 30 292.0 0.996 4.701 31 300.7 0.880 4.757 32 310.4 0.783 4.813 33 320.1 0.717 4.865 34 329.9 0.611 4.908

51

Sample

Pore Volumes

Concentration(mg/L)


35 339.6 0.530 4.946 36 349.3 0.417 4.976 37 358.9 0.403 5.004 38 371.7 0.331 5.036 39 384.5 0.290 5.063 40 396.1 0.239 5.083 41 410.2 0.227 5.107 42 459.2 0.135 5.156 43 476.1 0.159 5.176 44 490.8 0.111 5.188 45 503.7 0.097 5.197 46 518.6 0.080 5.205 47 533.1 0.074 5.213 48 547.3 0.069 5.220 49 561.6 0.073 5.228 50 591.1 0.044 5.238 51 605.8 0.040 5.242 52 635.6 0.043 5.251 53 665.3 0.025 5.257 54 692.6 0.024 5.262 55 721.9 0.022 5.267 56 889.7 0.014 5.284 57 1231.2 0.000 5.284 59 1252.9 0.000 5.284 60 1508.6 0.000 5.284 61 1609.8 0.000 5.284 62 2047.8 0.000 5.284 63 2270.6 0.000 5.284

52

Appendix Table A-4. Ethylbenzene removal data

Sample

Pore Volumes

Concentration(mg/L)


Start 0.0 0.000 0.000 1 1.5 2.403 0.026 2 9.9 2.293 0.168 3 18.4 1.811 0.281 4 27.7 2.773 0.473 5 35.5 2.118 0.593 6 46.1 2.958 0.824 7 53.7 1.998 0.936 8 63.1 1.762 1.058 9 72.0 1.687 1.169 10 81.6 1.879 1.301 11 90.2 2.564 1.464 12 99.0 2.338 1.615 13 108.4 2.559 1.793 14 120.9 1.672 1.946 15 129.2 1.836 2.058 16 138.0 1.781 2.174 17 147.4 2.629 2.355 18 156.8 2.194 2.507 19 166.2 2.068 2.650 20 175.8 2.003 2.791 21 185.2 1.842 2.919 22 194.7 2.278 3.078 23 205.7 2.191 3.256 24 216.8 2.034 3.421 25 226.4 2.122 3.572 26 252.2 2.625 4.070 27 261.8 2.400 4.240 28 272.5 2.258 4.418 29 281.2 2.251 4.563 30 292.0 2.116 4.729 31 300.7 2.096 4.865 32 310.4 2.134 5.017 33 320.1 2.315 5.183 34 329.9 2.232 5.342

53

Sample

Pore Volumes

Concentration(mg/L)


35 339.6 2.262 5.503 36 349.3 1.935 5.642 37 358.9 2.045 5.787 38 371.7 1.973 5.972 39 384.5 2.081 6.169 40 396.1 1.949 6.335 41 410.2 2.036 6.547 42 459.2 1.980 7.260 43 476.1 2.167 7.531 44 490.8 1.892 7.735 45 503.7 1.915 7.917 46 518.6 1.674 8.101 47 533.1 1.690 8.281 48 547.3 1.655 8.453 49 561.6 1.826 8.646 50 591.1 1.120 8.889 51 605.8 0.991 8.997 52 635.6 0.958 9.206 53 665.3 0.498 9.315 54 692.6 0.433 9.402 55 721.9 0.365 9.481 56 889.7 0.151 9.667 57 1231.2 0.087 9.885 59 1252.9 0.017 9.885 60 1508.6 0.006 9.887 61 1609.8 0.006 9.899 62 2047.8 0.000 9.903 63 2270.6 0.000 9.903

54

Appendix Table A-5. p-&m-xylene removal data

Sample

Pore Volumes

Concentration(mg/L)


Start 0.0 0.000 0.000 1 1.5 2.340 0.025 2 9.9 2.486 0.180 3 18.4 2.002 0.304 4 27.7 3.018 0.513 5 35.5 2.343 0.646 6 46.1 3.222 0.898 7 53.7 2.202 1.021 8 63.1 1.959 1.156 9 72.0 1.880 1.280 10 81.6 2.089 1.427 11 90.2 2.807 1.606 12 99.0 2.565 1.771 13 108.4 2.779 1.964 14 120.9 1.865 2.135 15 129.2 2.046 2.260 16 138.0 1.987 2.390 17 147.4 2.861 2.586 18 156.8 2.405 2.753 19 166.2 2.286 2.910 20 175.8 2.216 3.067 21 185.2 2.028 3.208 22 194.7 2.505 3.383 23 205.7 2.419 3.579 24 216.8 2.248 3.762 25 226.4 2.344 3.928 26 252.2 2.881 4.475 27 261.8 2.659 4.664 28 272.5 2.487 4.859 29 281.2 2.489 5.019 30 292.0 2.338 5.204 31 300.7 2.303 5.352 32 310.4 2.353 5.520 33 320.1 2.564 5.704 34 329.9 2.481 5.881

55

Sample

Pore Volumes

Concentration(mg/L)


35 339.6 2.516 6.060 36 349.3 2.150 6.214 37 358.9 2.275 6.375 38 371.7 2.216 6.584 39 384.5 2.327 6.804 40 396.1 2.225 6.993 41 410.2 2.318 7.235 42 459.2 2.429 8.109 43 476.1 2.677 8.444 44 490.8 2.508 8.715 45 503.7 2.621 8.963 46 518.6 2.432 9.230 47 533.1 2.591 9.506 48 547.3 2.700 9.788 49 561.6 3.124 10.118 50 591.1 2.237 10.603 51 605.8 2.120 10.833 52 635.6 2.234 11.322 53 665.3 1.283 11.603 54 692.6 1.147 11.834 55 721.9 0.959 12.040 56 889.7 0.343 12.464 57 1231.2 0.176 12.905 59 1252.9 0.042 12.905 60 1508.6 0.015 12.912 61 1609.8 0.015 12.940 62 2047.8 0.006 12.952 63 2270.6 0.000 12.972

56

Appendix Table A-6. o-xylene removal data

Sample

Pore Volumes

Concentration(mg/L)


Start 0.0 0.000 0.000 1 1.5 1.652 0.018 2 9.9 1.664 0.121 3 18.4 1.319 0.203 4 27.7 2.010 0.342 5 35.5 1.544 0.430 6 46.1 2.117 0.595 7 53.7 1.458 0.677 8 63.1 1.298 0.767 9 72.0 1.233 0.848 10 81.6 1.376 0.944 11 90.2 1.865 1.063 12 99.0 1.669 1.171 13 108.4 1.809 1.297 14 120.9 1.216 1.408 15 129.2 1.343 1.490 16 138.0 1.308 1.575 17 147.4 1.892 1.705 18 156.8 1.558 1.813 19 166.2 1.471 1.915 20 175.8 1.437 2.016 21 185.2 1.304 2.107 22 194.7 1.624 2.220 23 205.7 1.559 2.347 24 216.8 1.451 2.465 25 226.4 1.530 2.573 26 252.2 1.878 2.930 27 261.8 1.750 3.054 28 272.5 1.590 3.179 29 281.2 1.632 3.284 30 292.0 1.504 3.403 31 300.7 1.473 3.498 32 310.4 1.513 3.606 33 320.1 1.683 3.726 34 329.9 1.642 3.843

57

Sample

Pore Volumes

Concentration(mg/L)


35 339.6 1.663 3.962 36 349.3 1.377 4.060 37 358.9 1.450 4.163 38 371.7 1.410 4.296 39 384.5 1.531 4.440 40 396.1 1.461 4.565 41 410.2 1.504 4.722 42 459.2 1.537 5.275 43 476.1 1.724 5.490 44 490.8 1.636 5.667 45 503.7 1.767 5.835 46 518.6 1.649 6.016 47 533.1 1.820 6.210 48 547.3 1.957 6.414 49 561.6 2.391 6.667 50 591.1 1.998 7.099 51 605.8 2.083 7.326 52 635.6 2.747 7.927 53 665.3 1.983 8.361 54 692.6 2.118 8.787 55 721.9 2.038 9.226 56 889.7 0.554 9.911 57 1231.2 0.200 10.413 59 1252.9 0.019 10.413 60 1508.6 0.006 10.416 61 1609.8 0.007 10.428 62 2047.8 0.000 10.433 63 2270.6 0.000 10.433

58

Appendix Table A-7. BTEX BTC data for preliminary lab column with regenerated SMZ.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.0 0.000 0.001 0.004 0.007 0.005 2 8.0 0.034 0.001 0.004 0.007 0.006 3 15.5 0.747 0.002 0.004 0.006 0.005 4 23.0 0.961 0.159 0.004 0.006 0.004 5 28.6 0.976 0.441 0.003 0.005 0.001 6 36.0 0.952 0.675 0.003 0.004 0.003 7 46.8 0.964 0.763 0.015 0.007 0.023 8 55.7 0.961 0.772 0.075 0.024 0.096 9 64.5 0.901 0.717 0.183 0.082 0.210 10 84.0 0.995 0.805 0.388 0.269 0.414 11 100.9 1.003 0.922 0.529 0.441 0.555 12 110.5 0.983 0.939 0.602 0.523 0.629 13 119.4 1.014 1.002 0.669 0.600 0.688 14 130.5 1.029 1.004 0.720 0.663 0.741 15 141.9 1.002 0.979 0.733 0.682 0.754 16 152.6 0.941 0.976 0.764 0.709 0.778 17 165.1 1.054 1.038 0.838 0.798 0.854 18 186.1 1.001 0.816 0.833 0.811 0.850 19 205.0 1.001 0.941 0.810 0.785 0.805 20 213.1 0.963 0.864 0.742 0.742 0.750 21 224.7 0.997 0.906 0.759 0.750 0.768 22 235.7 0.954 0.941 0.792 0.776 0.810 23 247.5 0.934 0.926 0.745 0.731 0.761 24 259.6 0.965 0.949 0.743 0.726 0.751 25 269.9 0.976 0.936 0.746 0.724 0.753 26 289.4 1.001 0.954 0.775 0.750 0.787 27 309.7 1.028 0.989 0.832 0.790 0.827 28 320.3 1.023 0.997 0.838 0.813 0.838 29 333.8 1.011 0.980 0.834 0.818 0.825 30 351.0 1.024 0.995 0.869 0.846 0.862 31 370.6 1.012 0.986 0.863 0.837 0.866 32 405.9 0.994 0.945 0.822 0.808 0.816

59

APPENDIX B. COLUMN FLOW PROPERTIES, SMZ LOSS, AND SCANNING

ELECTRON MICROSCOPY INVESTIGATION OF SMZ PARTICLE

BREAKDOWN

COLUMN FLOW PROPERTIES: TRITIUM TRACER TEST

As described in the manuscript, a tritium tracer test was performed in each

column prior to the first sorption/regeneration cycle. The hydrodynamic properties of

each column determined from this test are presented in Appendix Table B-1. The tritium

BTCs on virgin SMZ for Columns 10B, 5A, and 5B are shown in Appendix Figures B-1,

B-2, and B-3, along with the fitted BTC for each column (using Eq. 2 described in the

manuscript). The tritium BTC for Column 10A is shown in the manuscript. The data

obtained from the virgin SMZ tritium tests in all four columns and the CXTFIT 2.1 fitted

data are shown in Appendix Table B-2.

At the conclusion of the sorption/regeneration cycles, before the SMZ was

removed from the columns for use in the batch sorption experiments, a second tritium

tracer test was conducted in each column. Because of high backpressures in the columns,

it was difficult to maintain a constant flow rate. The syringe pumps stalled occasionally

throughout the experiment, but they were restarted immediately in an attempt to maintain

a constant flow rate. The final hydrodynamic properties for each column are shown in

Appendix Table B-3, and the data from the second tracer test and CXTFIT 2.1 fitted data

are presented in Appendix Table B-4.

60

Appendix Table B-1. Hydrodynamic properties of laboratory columns before sorption cycles.

Mass SMZ (g)

Pore Volume (mL)

R P θ ρ (g/cm3)

Column 10A 5.11 3.24 1.13 30.5 0.64 1.016 Column 10B 5.09 3.43 1.05 31.2 0.68 1.012 Column 5A 4.90 3.20 0.955 24.1 0.64 0.974 Column 5B 5.12 3.28 1.07 26.4 0.65 1.018

61

0 2 4 6PORE VOLUMES OF PRODUCED WATER

0

0.2

0.4

0.6

0.8

1C

/C0

Appendix Figure B-1. Observed and fitted (Eq. 2) breakthrough curves for tritiated water in Column 10B.

62


0

0.2

0.4

0.6

0.8

1C

/C0

Appendix Figure B-2. Observed and fitted (Eq. 2) breakthrough curves for tritiated water in Column 5A.

63


0

0.2

0.4

0.6

0.8

1C

/C0

Appendix Figure B-3. Observed and fitted (Eq. 2) breakthrough curves for tritiated water in Column 5B.

64

Appendix Table B-2. Tritium breakthrough data for virgin SMZ.

Column 10A Column 10B Column 5A Column 5B

PV Obs. C/C0

Fit C/C0 PV

Obs. C/C0

Fit C/C0 PV

Obs. C/C0

Fit C/C0 PV

Obs. C/C0

Fit C/C0

0.131 0.000 0.000 0.107 0.000 0.000 0.119 0.000 0.000 0.109 0.000 0.000 0.362 0.000 0.000 0.307 0.000 0.000 0.342 0.000 0.000 0.320 0.001 0.000 0.565 0.000 0.004 0.507 0.001 0.002 0.546 0.027 0.033 0.521 0.000 0.005 0.773 0.054 0.085 0.693 0.035 0.063 0.755 0.238 0.247 0.718 0.043 0.092 0.986 0.366 0.341 0.867 0.243 0.265 0.968 0.597 0.575 0.924 0.340 0.346 1.192 0.694 0.633 1.046 0.589 0.548 1.170 0.825 0.803 1.129 0.661 0.633 1.401 0.828 0.836 1.227 0.791 0.775 1.375 0.930 0.923 1.331 0.828 0.828 1.633 0.904 0.944 1.403 0.902 0.902 1.829 0.948 0.993 1.530 0.865 0.928 1.885 0.878 0.985 1.629 0.902 0.971 2.022 0.949 0.998 1.722 0.938 0.972 2.072 0.945 0.995 1.787 0.937 0.989 2.226 0.973 0.999 1.915 0.919 0.990 2.275 0.963 0.998 1.967 0.950 0.996 2.430 0.899 0.959 2.113 0.966 0.996 2.474 0.955 0.967 2.148 0.954 0.982 2.638 0.774 0.732 2.315 0.956 0.960 2.686 0.838 0.777 2.309 0.901 0.875 2.853 0.402 0.403 2.514 0.810 0.772 2.888 0.489 0.486 2.500 0.602 0.601 3.058 0.177 0.181 2.706 0.453 0.496 3.086 0.225 0.246 2.695 0.298 0.314 3.263 0.086 0.070 2.905 0.220 0.255 3.300 0.104 0.099 2.875 0.150 0.143 3.475 0.049 0.024 3.109 0.114 0.111 3.502 0.058 0.037 3.066 0.071 0.054 3.670 0.030 0.008 3.310 0.069 0.044 3.705 0.037 0.013 3.250 0.041 0.019 3.874 0.019 0.003 3.512 0.044 0.016 3.899 0.024 0.004 3.436 0.026 0.006 4.035 0.014 0.001 3.716 0.026 0.005 4.092 0.019 0.001 3.627 0.017 0.002 4.372 0.014 0.000 3.920 0.020 0.002 4.396 0.015 0.000 3.836 0.015 0.001 4.584 0.012 0.000 4.075 0.023 0.001 4.610 0.013 0.000 4.001 0.013 0.000 4.790 0.009 0.000 4.412 0.014 0.000 4.816 0.010 0.000 4.201 0.010 0.000 4.985 0.007 0.000 4.609 0.012 0.000 5.024 0.008 0.000 4.389 0.006 0.000 5.181 0.005 0.000 4.807 0.009 0.000 5.235 0.006 0.000 4.585 0.006 0.000 5.388 0.004 0.000 5.006 0.007 0.000 5.442 0.004 0.000 4.799 0.004 0.000 5.600 0.002 0.000 5.209 0.005 0.000 5.658 0.003 0.000 4.995 0.003 0.000 5.809 0.001 0.000 5.409 0.003 0.000 5.857 0.002 0.000 5.174 0.002 0.000 6.013 0.001 0.000 5.610 0.002 0.000 6.041 0.002 0.000 5.363 0.001 0.000 6.214 0.001 0.000 5.812 0.002 0.000 6.245 0.001 0.000 5.557 0.002 0.000 6.417 0.001 0.000 6.013 0.001 0.000 6.451 0.001 0.000 5.753 0.001 0.000 6.593 0.001 0.000 6.217 0.001 0.000 6.665 0.001 0.000 5.951 0.001 0.000 6.421 0.001 0.000

65

Appendix Table B-3. Hydrodynamic properties of laboratory columns after sorption cycles.

Mass SMZ (g)

% SMZ Lost R P θ ρ (g/cm3)

Column 10A 5.06 0.98 0.94 17.1 0.70 1.012 Column 10B 3.65 28.3 0.88 6.85 0.87 1.726 Column 5A 4.83 1.43 0.93 15.6 0.76 0.960 Column 5B 4.72 7.81 0.93 14.2 0.70 0.938

66

Appendix Table B-4. Tritium breakthrough data after sorption cycles.

Column 10A Column 10B Column 5A Column 5B

PV Obs. C/C0

Fit C/C0 PV

Obs. C/C0

Fit C/C0 PV

Obs. C/C0

Fit C/C0 PV

Obs. C/C0

Fit C/C0

0.281 0.000 0.000 0.081 0.000 0.000 0.091 0.000 0.000 0.089 0.000 0.000 0.464 0.008 0.025 0.240 0.000 0.008 0.272 0.000 0.000 0.267 0.000 0.000 0.650 0.125 0.177 0.397 0.027 0.097 0.448 0.013 0.028 0.449 0.005 0.032 0.837 0.413 0.432 0.553 0.230 0.263 0.620 0.119 0.167 0.633 0.133 0.191 1.024 0.665 0.665 0.712 0.477 0.444 0.787 0.378 0.390 0.819 0.462 0.433 1.302 0.858 0.873 0.874 0.554 0.599 0.959 0.640 0.609 1.007 0.718 0.652 1.471 0.929 0.934 1.034 0.733 0.717 1.130 0.784 0.771 1.193 0.812 0.803 1.654 0.956 0.967 1.196 0.808 0.803 1.412 0.930 0.916 1.378 0.867 0.894 1.834 0.912 0.922 1.394 0.838 0.875 1.579 0.943 0.956 1.554 0.882 0.943 2.143 0.518 0.555 1.553 0.881 0.902 1.752 0.942 0.957 1.732 0.932 0.970 2.305 0.313 0.353 1.714 0.830 0.827 1.926 0.784 0.838 1.918 0.943 0.965 2.464 0.198 0.209 1.872 0.699 0.672 2.098 0.641 0.618 2.107 0.880 0.832 2.636 0.123 0.111 2.030 0.475 0.508 2.266 0.405 0.403 2.298 0.591 0.593 2.931 0.059 0.034 2.191 0.311 0.367 2.436 0.229 0.239 2.484 0.338 0.370 3.104 0.044 0.016 2.354 0.209 0.257 2.603 0.135 0.135 2.670 0.194 0.212 3.278 0.032 0.008 2.518 0.149 0.178 2.771 0.080 0.072 2.857 0.128 0.114 3.564 0.021 0.002 2.684 0.110 0.122 2.946 0.050 0.037 3.046 0.091 0.058 3.726 0.018 0.001 2.849 0.090 0.083 3.120 0.040 0.018 3.234 0.071 0.029 3.900 0.015 0.001 3.012 0.075 0.057 3.291 0.028 0.009 3.420 0.054 0.015 4.067 0.012 0.000 3.175 0.066 0.039 3.587 0.022 0.003 3.608 0.043 0.007 4.223 0.009 0.000 3.324 0.058 0.028 3.750 0.017 0.001 3.780 0.035 0.004 4.380 0.007 0.000 3.480 0.057 0.019 3.925 0.013 0.001 3.965 0.030 0.002

3.654 0.053 0.013 4.101 0.011 0.000 4.161 0.026 0.001 3.819 0.055 0.009 4.276 0.009 0.000 4.341 0.022 0.000 3.982 0.046 0.006 4.450 0.007 0.000 4.525 0.020 0.000 4.148 0.037 0.004 4.624 0.006 0.000 4.715 0.015 0.000 4.308 0.026 0.003 4.800 0.003 0.000 4.910 0.011 0.000 4.470 0.018 0.002 4.971 0.004 0.000 5.099 0.008 0.000 4.636 0.014 0.001 5.147 0.003 0.000 5.288 0.006 0.000 4.797 0.013 0.001 5.326 0.002 0.000 5.478 0.005 0.000 4.959 0.011 0.001 5.500 0.002 0.000 5.664 0.006 0.000 5.123 0.010 0.001 5.655 0.002 0.000 5.850 0.004 0.000

67

SMZ LOSS AND SMZ PARTICLE BREAKDOWN: SCANNING ELECTRON

MICROSCOPY

With increasing sorption cycles, loss of SMZ from Columns 10B, 5A, and 5B was

apparent. It is believed that the nylon mesh placed just inside the column end-fittings

became dislodged, allowed SMZ to escape out the end-fittings. Some SMZ was observed

in both influent and effluent tubing from these columns. As shown in Appendix Table B-

3, all four columns had lost SMZ ranging in amount from 0.98% to 28.3% of the initial

amount. The nylon mesh covering the end-fittings in Column 10A had not dislodged and

this column experienced little SMZ loss (0.98%). This indicates that the nylon does hold

most of the SMZ inside the columns, and should be more permanently attached the end-

fittings in the future to prevent it from moving out of place.

Another concern that arose with increasing sorption cycles performed was that

backpressures increased in each column. This issue was discussed briefly in the

manuscript. The SEM images used to investigate the backpressure increase are presented

below, along with additional conclusions from this work not discussed in the manuscript.

To investigate the reason for the increase of backpressure in the laboratory

columns during the final sorption/regeneration cycles, the SMZ removed from each

column was examined with a scanning electron microscope (SEM). The following series

of images were acquired from SMZ that had not been previously exposed to SMZ, SMZ

from Column 5A, and SMZ from Columns 10A and 10B. The three image series were

obtained at 3 different magnifications, 35X, 190X, and 4500X.

68

The 35X and 190X images show that the average particle size of SMZ in

Columns 5A, 10A, and 10B has decreased significantly from the virgin SMZ. Continued

use of the SMZ in the column systems likely led to grain damage, creating abundant fine

grained particles which reduced the column permeability and raised backpressures.

Appendix Figure B-4 shows that many virgin SMZ particles are 100 µm or greater in

diameter, while Appendix Figure B-10 shows that few SMZ particles from column 10B

are this large. Closer inspection of the largest grains in Appendix Figure B-10 revealed

that many of these particles are not SMZ, but are other material including quartz and

volcanic glass. Appendix Figure B-11 shows that in Column 10B, a significant portion of

SMZ particles are 10 µm or less in diameter, while fewer virgin SMZ particles are this

small (Appendix Figure B-5). The images at 4500X (Appendix Figures B-6, B-9, and B-

12) show that the SMZ particles consist of the same structure in all the SMZ samples.

Zeolite (clinoptilolite) crystals are the cubes and plates seen in the images, and each

figure contains other minerals (likely clays or other amorphous zeolites) present on the

SMZ surface.

The cause of the particle breakdown could be either mechanical or chemical in

origin. Future work addressing this issue is necessary, as the high backpressures were the

limiting factor determining the length of use of the laboratory system. If the reason is

mechanical, a system design that would reduce the differential stress on the SMZ

particles and therefore reduce the likelihood of significant SMZ particle breakdown is

needed. However, if the reason is chemical, additional work is needed to determine the

specific reasons for particle breakdown and possible solutions. To potentially delay the

high backpressure effects of SMZ particle breakdown, using an initial SMZ grain size

69

with larger pores could allow more fine-grained particles to pass through the system

before clogging pores and raising permeability. However, this practice could result in

buildup of fine particles on the nylon mesh covering the column end-fittings or the loss of

SMZ material from the columns.

The SEM work was conducted at Los Alamos National Laboratory (LANL),

using a JEOL Model JSM-6300FXV SEM. Jim Smith and E. Jeri Sullivan of LANL

assisted with the analysis. The samples were prepared for microscopy by affixing the

SMZ to double-sided carbon tape and coating the samples with carbon. The following

images were acquired at 1.0 kV accelerating voltage using secondary imaging and a

working distance of 15 mm.

70

Appendix Figure B-4. SEM image of virgin SMZ (35X).

71

Appendix Figure B-5. SEM image of virgin SMZ (190X). Large particle in upper-center is quartz.

72

Appendix Figure B-6. SEM image of virgin SMZ (4500X).

73

Appendix Figure B-7. SEM image of Column 5A SMZ (35X).

74


75


76

Appendix Figure B-10. SEM image of Column 10B SMZ (35X).

77

Appendix Figure B-11. SEM image of Column 10B SMZ (190X).

78


79

APPENDIX C. LABORATORY COLUMN BTC DATA

Figure 4 of the manuscript shows the 10 BTCs of benzene and p-&m-xylene in

Column 10A. The BTCs for the other compounds in Column 10A are shown in

Appendix Figures C-1 through C-3. The BTCs for each compound in Column 10B are

plotted in Appendix Figures C-4 through C-8. As discussed in the manuscript, the

column experiments show no significant loss of SMZ sorption capacity after 10

sorption/regeneration cycles. However, during the third sorption cycle in Columns 10A

and 10B, ethylbenzene and o-xylene do have a different BTC than during the other

cycles. The reason the C/C0 measurements for these two compounds are lower than

expected during BTC 3 is because additional ethylbenzene and o-xylene were added to

the produced water in the bag, as discussed in the manuscript. During BTC 3, these

compounds were not equilibrated in the sampling bag and their influent concentrations

were increasing throughout the injection cycle. Because C0 was rising, C/C0 was

decreased, lowering the points on the BTC.

Appendix Tables C-1 through C-10 contain the data for the 10 BTEX BTCs from

Column 10A, and Appendix Tables C-11 through C-20 contain the data for the 10 BTEX

BTCs from Column 10B. Appendix Tables C-21 through C-30 provide the data from the

10 sparging cycles for Column 10A, and Appendix Tables C-31 through C-40 contain the

data from the 10 sparging cycles for Column 10B.

Appendix Tables C-41 and C-42 contains the Kd determined during each sorption

cycle in Columns 10A and 10B, and also the estimated mass of each BTEX compound

retained by the SMZ during sorption, the estimated mass of each BTEX compound

80

removed from the SMZ during each regeneration cycle, and the apparent cumulative

mass of each compound present on the SMZ following the sorption/regeneration cycle.

The reason why more o-xylene is removed during sparging than is sorbed is unclear,

although it is hypothesized that another compound present in the exhaust gas co-elutes

with o-xylene in the GC analysis.

Appendix Table C-43 contains the CXTFIT 2.1 calculations used to create Figure

2 in the manuscript.

81


0

0.2

0.4

0.6

0.8

1C

/C0


Appendix Figure C-1. Toluene BTCs for Column 10A over 10 sorption/regeneration cycles.

82


0

0.2

0.4

0.6

0.8

1C

/C0 BTC 1

BTC 2BTC 3BTC 4BTC 5BTC 6BTC 7BTC 8BTC 9BTC 10

Appendix Figure C-2. Ethylbenzene BTCs for Column 10A over 10 sorption/regeneration cycles.

83


0

0.2

0.4

0.6

0.8

1C

/C0 BTC 1


Appendix Figure C-3. o-xylene BTCs for Column 10A over 10 sorption/regeneration cycles.

84


0

0.2

0.4

0.6

0.8

1C

/C0


Appendix Figure C-4. Benzene BTCs for Column 10B over 10 sorption/regeneration cycles.

85


0

0.2

0.4

0.6

0.8

1C

/C0


Appendix Figure C-5. Toluene BTCs for Column 10B over 10 sorption/regeneration cycles.

86


0

0.2

0.4

0.6

0.8

1C

/C0 BTC 1


Appendix Figure C-6. Ethylbenzene BTCs for Column 10B over 10 sorption/regeneration cycles.

87


0

0.2

0.4

0.6

0.8

1C

/C0


Appendix Figure C-7. p-&m-xylene BTCs for Column 10B over 10 sorption/regeneration cycles.

88


0

0.2

0.4

0.6

0.8

1C

/C0 BTC 1


Appendix Figure C-8. o-xylene BTCs for Column 10B over 10 sorption/regeneration cycles.

89

Appendix Table C-1. Data for BTEX BTC 1 from Column 10A.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.8 0.020 0.018 0.027 0.052 0.125 2 6.7 0.130 0.019 0.026 0.051 0.128 3 10.4 0.524 0.022 0.024 0.046 0.120 4 14.5 0.771 0.046 0.024 0.045 0.117 5 18.6 0.879 0.133 0.023 0.045 0.116 6 30.3 0.898 0.516 0.024 0.051 0.111 7 41.9 0.930 0.737 0.037 0.043 0.114 8 53.4 0.979 0.838 0.107 0.078 0.186 9 64.8 1.022 0.921 0.241 0.171 0.315 10 76.0 0.973 0.863 0.344 0.261 0.399 11 87.1 1.062 0.963 0.505 0.422 0.561 12 134.1 1.019 0.983 0.717 0.671 0.741 13 207.0 0.939 0.899 0.758 0.740 0.767 14 254.0 0.945 0.936 0.818 0.792 0.817 15 307.3 0.920 0.914 0.824 0.810 0.828 16 346.4 0.947 0.945 0.876 0.877 0.898 17 389.4 0.951 0.942 0.870 0.862 0.872 18 417.0 0.977 0.976 0.911 0.893 0.913

90


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 1.3 0.013 0.017 0.032 0.028 0.012 2 4.2 0.017 0.014 0.029 0.020 0.008 3 8.2 0.184 0.015 0.035 0.021 0.009 4 12.3 0.511 0.025 0.037 0.022 0.010 5 15.7 0.754 0.055 0.043 0.025 0.011 6 19.8 0.709 0.107 0.045 0.033 0.016 7 31.8 0.807 0.411 0.054 0.031 0.016 8 46.6 0.841 0.656 0.093 0.052 0.039 9 61.1 0.880 0.754 0.170 0.103 0.107 10 75.4 0.854 0.771 0.180 0.175 0.151 11 89.9 0.903 0.850 0.238 0.295 0.227 12 106.8 0.868 0.816 0.293 0.369 0.294 13 156.4 0.944 0.915 0.527 0.624 0.551 14 197.2 0.918 0.891 0.707 0.673 0.735 15 266.2 0.951 0.943 0.859 0.803 0.871 16 331.9 1.032 1.004 0.913 0.910 0.911 17 412.0 1.001 0.991 0.774 0.919 0.795

91


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 0.9 0.016 0.017 0.034 0.030 0.031 2 4.3 0.022 0.018 0.032 0.022 0.034 3 7.8 0.174 0.022 0.046 0.028 0.051 4 11.6 0.458 0.028 0.051 0.031 0.059 5 16.1 0.713 0.050 0.054 0.037 0.065 6 25.1 0.880 0.214 0.065 0.056 0.078 7 40.1 0.867 0.544 0.063 0.054 0.075 8 54.7 0.916 0.742 0.092 0.083 0.107 9 69.0 0.817 0.700 0.111 0.116 0.125 10 82.8 0.898 0.802 0.136 0.204 0.147 11 130.5 0.887 0.837 0.331 0.452 0.348 12 186.8 0.928 0.897 0.586 0.645 0.600 13 237.2 0.996 0.977 0.810 0.815 0.811 14 275.0 0.908 0.884 0.721 0.746 0.722 15 319.7 0.932 0.933 0.835 0.803 0.839 16 359.6 0.977 0.943 0.801 0.844 0.801 17 389.3 0.962 0.955 0.808 0.865 0.818 18 436.0 1.047 1.026 0.926 0.943 0.928 19 480.6 0.955 0.943 0.881 0.864 0.895

92


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.2 0.067 0.071 0.093 0.099 0.103 2 5.8 0.092 0.078 0.093 0.095 0.103 3 9.4 0.261 0.083 0.088 0.087 0.099 4 13.1 0.523 0.099 0.092 0.090 0.104 5 16.7 0.676 0.119 0.093 0.090 0.106 6 29.9 0.853 0.319 0.117 0.114 0.133 7 45.2 0.884 0.589 0.148 0.130 0.168 8 57.7 0.911 0.723 0.191 0.160 0.219 9 74.6 0.899 0.775 0.259 0.209 0.287 10 118.2 0.944 0.879 0.499 0.426 0.522 11 160.3 0.950 0.891 0.660 0.609 0.671 12 205.0 0.990 0.952 0.814 0.783 0.827 13 258.1 1.020 0.978 0.903 0.860 0.908 14 299.6 0.988 0.958 0.809 0.849 0.817 15 347.7 1.006 0.979 0.854 0.892 0.867 16 393.2 0.961 0.934 0.837 0.857 0.839 17 437.2 0.952 0.946 0.867 0.890 0.872 18 468.4 0.990 0.977 0.940 0.927 0.938

93


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 1.7 0.015 0.022 0.029 0.032 0.023 2 5.4 0.043 0.023 0.030 0.027 0.026 3 9.3 0.299 0.030 0.043 0.037 0.040 4 13.3 0.527 0.038 0.045 0.039 0.044 5 17.3 0.681 0.069 0.051 0.044 0.050 6 31.2 0.832 0.333 0.060 0.053 0.060 7 47.1 0.891 0.612 0.085 0.066 0.086 8 62.9 0.899 0.724 0.142 0.101 0.141 9 80.8 0.887 0.763 0.232 0.169 0.231 10 131.0 0.956 0.892 0.539 0.469 0.551 11 171.5 1.008 0.963 0.733 0.701 0.735 12 219.7 0.973 0.949 0.795 0.786 0.804 13 269.8 0.986 0.956 0.853 0.871 0.858 14 315.3 0.958 0.937 0.831 0.851 0.844 15 351.7 0.987 0.974 0.885 0.897 0.893 16 396.0 1.002 1.001 0.920 0.943 0.930 17 441.9 0.986 0.989 0.917 0.936 0.923 18 476.2 0.982 0.972 0.895 0.907 0.905

94


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 1.9 0.026 0.037 0.032 0.051 0.043 2 5.8 0.063 0.031 0.036 0.041 0.043 3 9.6 0.292 0.036 0.043 0.046 0.053 4 13.4 0.541 0.052 0.049 0.051 0.061 5 17.2 0.679 0.088 0.052 0.053 0.065 6 32.9 0.872 0.403 0.071 0.076 0.089 7 46.0 0.878 0.597 0.096 0.082 0.114 8 56.6 0.917 0.719 0.146 0.113 0.165 9 77.4 0.952 0.829 0.276 0.210 0.297 10 110.3 0.931 0.859 0.470 0.392 0.491 11 156.5 0.949 0.911 0.692 0.651 0.720 12 207.6 0.991 0.961 0.829 0.837 0.861 13 253.0 0.914 0.889 0.760 0.786 0.793 14 308.2 0.979 0.972 0.849 0.887 0.880 15 355.1 0.999 0.990 0.870 0.916 0.897 16 394.0 0.994 0.976 0.854 0.912 0.878 17 437.2 1.017 1.013 0.882 0.967 0.908 18 465.4 1.007 0.996 0.936 0.963 0.957

95


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.0 0.022 0.032 0.034 0.042 0.032 2 5.7 0.071 0.035 0.035 0.036 0.034 3 9.4 0.315 0.041 0.044 0.043 0.045 4 13.1 0.536 0.055 0.049 0.049 0.053 5 16.8 0.684 0.092 0.054 0.054 0.059 6 34.8 0.840 0.430 0.070 0.074 0.078 7 50.1 0.900 0.667 0.108 0.096 0.117 8 63.1 0.913 0.759 0.167 0.139 0.177 9 83.0 0.942 0.847 0.297 0.251 0.305 10 123.3 0.986 0.932 0.573 0.528 0.582 11 167.6 0.974 0.941 0.744 0.727 0.756 12 204.3 1.016 0.998 0.855 0.843 0.867 13 255.8 0.986 0.957 0.859 0.876 0.875 14 309.2 0.998 0.988 0.879 0.919 0.895 15 356.3 1.026 1.025 0.894 0.956 0.915 16 399.5 0.995 0.984 0.841 0.936 0.863 17 439.2 1.026 1.042 0.900 1.011 0.925 18 472.3 1.008 0.997 0.900 0.967 0.915

96


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.0 0.016 0.024 0.028 0.035 0.027 2 5.8 0.047 0.024 0.028 0.028 0.028 3 9.8 0.302 0.042 0.055 0.051 0.055 4 13.8 0.567 0.060 0.064 0.059 0.065 5 17.6 0.712 0.100 0.068 0.063 0.071 6 31.7 0.828 0.365 0.078 0.076 0.081 7 48.5 0.905 0.646 0.117 0.095 0.121 8 72.6 0.953 0.813 0.260 0.199 0.257 9 110.5 0.928 0.860 0.503 0.428 0.498 10 163.2 0.990 0.949 0.747 0.719 0.748 11 207.7 0.946 0.926 0.797 0.787 0.802 12 246.2 0.931 0.897 0.813 0.822 0.816 13 291.5 1.000 0.977 0.884 0.901 0.891 14 335.8 0.981 0.961 0.866 0.880 0.868 15 379.5 0.938 0.920 0.832 0.857 0.850 16 418.1 0.971 0.969 0.870 0.926 0.892 17 440.1 0.978 0.975 0.872 0.934 0.894 18 470.9 0.995 1.000 0.893 0.970 0.919

97


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 1.5 0.024 0.034 0.035 0.040 0.030 2 5.0 0.054 0.036 0.034 0.032 0.033 3 8.4 0.227 0.042 0.042 0.038 0.044 4 11.7 0.467 0.055 0.050 0.046 0.054 5 15.5 0.628 0.085 0.057 0.052 0.062 6 31.4 0.847 0.413 0.082 0.079 0.089 7 45.0 0.828 0.589 0.105 0.086 0.112 8 62.9 0.906 0.774 0.202 0.154 0.209 9 75.8 0.895 0.807 0.289 0.220 0.295 10 97.6 0.886 0.819 0.424 0.345 0.435 11 138.4 0.966 0.933 0.694 0.623 0.708 12 189.7 1.000 0.973 0.825 0.782 0.842 13 220.7 1.008 0.997 0.874 0.848 0.900 14 258.9 1.004 0.981 0.879 0.868 0.905 15 304.4 0.981 0.964 0.889 0.896 0.921 16 352.9 0.990 0.970 0.856 0.925 0.878 17 405.7 1.011 0.991 0.885 0.938 0.893 18 447.9 1.038 1.020 0.923 0.973 0.928

98


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.0 0.021 0.032 0.029 0.031 0.029 2 5.9 0.091 0.037 0.035 0.034 0.039 3 10.0 0.329 0.047 0.043 0.040 0.051 4 13.9 0.579 0.075 0.051 0.048 0.063 5 17.9 0.710 0.126 0.057 0.053 0.071 6 37.3 0.885 0.523 0.094 0.085 0.113 7 54.0 0.872 0.705 0.159 0.128 0.179 8 70.0 0.904 0.813 0.267 0.216 0.284 9 99.9 0.920 0.864 0.476 0.418 0.493 10 141.9 0.976 0.930 0.670 0.643 0.676 11 192.8 0.972 0.942 0.780 0.772 0.792 12 231.6 0.968 0.947 0.815 0.827 0.833 13 240.6 1.014 0.986 0.865 0.876 0.871

99

Appendix Table C-11. Data for BTEX BTC 1 from Column 10B.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 5.9 0.047 0.032 0.009 0.021 0.045 2 9.0 0.382 0.010 0.008 0.018 0.040 3 12.4 0.659 0.020 0.007 0.016 0.038 4 18.7 0.801 0.114 0.007 0.014 0.034 5 22.5 0.889 0.242 0.006 0.014 0.034 6 29.8 0.900 0.506 0.009 0.018 0.037 7 39.9 0.911 0.700 0.021 0.020 0.049 8 51.2 0.945 0.788 0.103 0.065 0.143 9 62.0 0.935 0.841 0.195 0.127 0.231 10 73.1 0.970 0.906 0.355 0.261 0.388 11 149.0 0.963 0.918 0.726 0.692 0.733 12 200.3 1.047 1.033 0.883 0.861 0.887 13 264.5 0.879 0.866 0.774 0.766 0.786 14 308.4 0.969 0.969 0.905 0.891 0.894 15 352.1 0.867 0.861 0.817 0.806 0.818 16 438.7 0.877 0.874 0.825 0.825 0.829

100


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 1.1 0.012 0.014 0.035 0.035 0.016 2 4.5 0.023 0.010 0.023 0.018 0.008 3 8.2 0.191 0.011 0.022 0.015 0.006 4 12.3 0.598 0.021 0.023 0.016 0.007 5 17.6 0.745 0.074 0.023 0.014 0.006 6 21.9 0.821 0.181 0.032 0.027 0.013 7 31.9 0.907 0.502 0.044 0.031 0.015 8 46.2 0.935 0.738 0.097 0.097 0.126 9 58.0 0.946 0.824 0.112 0.109 0.081 10 69.8 0.925 0.815 0.167 0.176 0.141 11 85.1 0.978 0.899 0.282 0.324 0.268 12 132.2 0.906 0.844 0.504 0.524 0.521 13 177.4 0.979 0.927 0.777 0.694 0.802 14 249.4 1.051 1.033 0.971 0.909 0.975 15 316.5 0.951 0.935 0.862 0.851 0.849 16 401.4 0.943 0.933 0.744 0.881 0.773 17 432.3 0.980 0.972 0.865 0.930 0.844

101


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.3 0.028 0.010 0.024 0.019 0.023 2 6.0 0.077 0.012 0.026 0.017 0.030 3 9.9 0.371 0.022 0.035 0.022 0.042 4 13.9 0.613 0.043 0.035 0.021 0.043 5 17.7 0.732 0.091 0.041 0.023 0.049 6 21.5 0.786 0.176 0.061 0.042 0.073 7 36.1 0.739 0.449 0.079 0.045 0.094 8 51.7 0.853 0.700 0.128 0.085 0.145 9 67.8 0.845 0.745 0.159 0.149 0.174 10 83.4 0.952 0.889 0.246 0.279 0.260 11 133.9 0.951 0.898 0.326 0.580 0.336 12 186.7 0.956 0.912 0.584 0.712 0.592 13 225.8 0.993 0.966 0.707 0.800 0.711 14 274.0 0.995 0.945 0.767 0.811 0.761 15 317.2 0.980 0.941 0.828 0.827 0.825 16 362.6 0.996 0.963 0.878 0.865 0.872 17 408.4 0.981 0.969 0.818 0.885 0.828 18 458.8 1.001 0.998 0.914 0.931 0.925

102


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.1 0.086 0.044 0.047 0.055 0.055 2 5.7 0.178 0.056 0.051 0.055 0.057 3 9.2 no data no data no data no data no data 4 12.9 no data no data no data no data no data 5 16.4 no data no data no data no data no data 6 31.7 0.916 0.514 0.122 0.114 0.132 7 42.1 0.845 0.612 0.144 0.120 0.154 8 56.6 0.877 0.737 0.225 0.178 0.241 9 71.8 0.878 0.780 0.310 0.246 0.333 10 93.9 0.900 0.841 0.458 0.374 0.483 11 138.3 0.936 0.912 0.706 0.652 0.728 12 179.4 0.947 0.947 0.835 0.809 0.850 13 222.3 0.978 0.968 0.905 0.893 0.923 14 276.0 0.933 0.920 0.886 0.854 0.894 15 317.9 0.934 0.923 0.806 0.850 0.821 16 362.1 0.947 0.928 0.833 0.874 0.847 17 408.9 0.938 0.918 0.841 0.863 0.847 18 451.3 0.942 0.928 0.862 0.885 0.871

103


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 1.6 0.019 0.020 0.062 0.076 0.082 2 5.1 0.068 0.018 0.052 0.057 0.067 3 8.8 0.309 0.022 0.046 0.049 0.057 4 12.6 0.622 0.049 0.049 0.051 0.058 5 16.4 0.757 0.102 0.049 0.050 0.057 6 32.6 0.811 0.443 0.061 0.055 0.065 7 46.3 0.882 0.678 0.110 0.080 0.111 8 67.4 0.925 0.815 0.252 0.178 0.251 9 85.9 0.913 0.846 0.390 0.299 0.392 10 104.4 0.964 0.913 0.548 0.455 0.548 11 152.4 0.929 0.903 0.737 0.706 0.745 12 196.4 0.890 0.964 0.868 0.849 0.854 13 242.9 0.942 0.923 0.848 0.851 0.853 14 289.4 0.994 0.974 0.949 0.972 0.945 15 312.1 1.002 1.015 1.018 1.038 1.016 16 332.1 0.946 0.941 0.923 0.948 0.923 17 380.6 0.938 0.900 0.852 0.879 0.857 18 425.3 1.046 1.036 0.951 0.962 0.948 19 454.8 0.931 0.920 0.840 0.847 0.851

104


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.9 0.036 0.021 0.036 0.042 0.037 2 5.6 0.096 0.019 0.033 0.035 0.036 3 10.0 0.440 0.029 0.031 0.033 0.037 4 12.6 0.614 0.051 0.034 0.035 0.041 5 16.3 0.808 0.118 0.043 0.044 0.052 6 32.8 0.909 0.542 0.070 0.065 0.082 7 54.8 0.885 0.760 0.180 0.130 0.196 8 70.7 0.924 0.840 0.324 0.238 0.340 9 84.9 0.987 0.939 0.501 0.393 0.521 10 133.6 0.898 0.875 0.710 0.646 0.724 11 181.7 0.955 0.927 0.851 0.841 0.862 12 226.0 0.911 0.885 0.792 0.803 0.805 13 239.5 0.999 1.002 0.919 0.936 0.930 14 274.9 0.955 0.935 0.860 0.908 0.864 15 317.2 0.977 0.965 0.869 0.928 0.881 16 360.2 1.039 1.035 0.916 0.991 0.922 17 406.0 0.931 0.920 0.845 0.875 0.856 18 450.5 0.943 0.936 0.866 0.903 0.869

105


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 3.1 0.046 0.022 0.038 0.044 0.040 2 6.6 0.338 0.041 0.040 0.043 0.043 3 10.3 0.633 0.090 0.041 0.043 0.045 4 14.0 0.827 0.196 0.047 0.047 0.051 5 17.7 0.803 0.301 0.050 0.047 0.055 6 33.5 0.893 0.682 0.142 0.119 0.146 7 49.4 0.863 0.767 0.275 0.222 0.279 8 57.8 0.950 0.879 0.395 0.332 0.398 9 73.6 0.953 0.906 0.529 0.483 0.539 10 108.7 0.967 0.939 0.735 0.727 0.744 11 151.9 0.970 0.964 0.875 0.877 0.881 12 200.4 0.986 0.970 0.905 0.898 0.911 13 240.5 1.006 1.001 0.962 0.957 0.963 14 290.3 0.953 0.938 0.899 0.920 0.911 15 340.0 1.014 1.011 0.947 0.977 0.963 16 384.6 0.925 0.907 0.832 0.877 0.847 17 426.9 0.965 0.966 0.882 0.952 0.894 18 454.7 0.974 0.970 0.875 0.955 0.887

106


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 3.0 0.061 0.038 0.084 0.087 0.085 2 6.4 0.426 0.065 0.079 0.080 0.080 3 10.0 0.694 0.131 0.071 0.069 0.071 4 13.6 0.793 0.233 0.069 0.065 0.070 5 17.2 0.857 0.356 0.078 0.069 0.079 6 30.1 0.893 0.686 0.170 0.143 0.171 7 50.8 0.957 0.891 0.433 0.358 0.428 8 67.3 1.014 0.966 0.618 0.541 0.611 9 92.0 0.952 0.929 0.740 0.683 0.739 10 128.5 0.940 0.942 0.843 0.819 0.851 11 175.4 0.984 0.969 0.896 0.909 0.897 12 221.7 0.994 0.986 0.938 0.938 0.940 13 258.2 1.024 1.013 0.993 1.001 0.981 14 302.4 1.027 1.024 0.978 0.987 0.978 15 346.8 1.045 1.044 0.987 1.012 0.991 16 391.5 0.959 0.959 0.926 0.944 0.943 17 429.0 0.991 0.999 0.955 0.993 0.960 18 452.1 0.987 0.989 0.906 0.983 0.930

107


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.9 0.082 0.024 0.035 0.040 0.034 2 6.3 0.469 0.072 0.041 0.042 0.043 3 9.9 0.739 0.174 0.051 0.048 0.053 4 13.3 0.834 0.295 0.065 0.057 0.066 5 16.8 0.838 0.382 0.074 0.062 0.076 6 32.3 0.894 0.699 0.207 0.172 0.203 7 45.1 0.916 0.801 0.350 0.292 0.344 8 55.5 0.932 0.843 0.459 0.396 0.456 9 68.0 0.979 0.921 0.614 0.550 0.605 10 86.1 0.921 0.880 0.685 0.641 0.691 11 118.1 0.977 0.941 0.829 0.822 0.830 12 160.6 0.959 0.940 0.872 0.886 0.875 13 210.3 0.915 0.922 0.880 0.903 0.892 14 241.4 0.959 0.942 0.893 0.924 0.896 15 281.4 0.906 0.880 0.897 0.935 0.904 16 325.9 0.991 0.966 0.917 0.969 0.922 17 374.8 0.960 0.953 0.887 0.936 0.899 18 430.8 0.974 0.956 0.920 0.947 0.918 19 448.2 1.020 1.011 0.969 0.991 0.976

108


Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 2.9 0.084 0.031 0.043 0.050 0.049 2 6.4 0.440 0.098 0.054 0.055 0.062 3 9.8 0.611 0.178 0.061 0.059 0.071 4 13.3 0.759 0.302 0.084 0.076 0.095 5 16.7 0.750 0.395 0.107 0.093 0.120 6 32.1 0.965 0.761 0.284 0.234 0.302 7 47.3 0.953 0.856 0.462 0.388 0.482 8 57.7 1.062 0.964 0.610 0.526 0.624 9 73.0 1.054 0.958 0.689 0.624 0.713 10 119.3 1.034 0.992 0.870 0.858 0.878 11 160.3 0.975 0.957 0.899 0.915 0.908 12 189.7 0.962 0.930 0.887 0.906 0.885 13 195.4 0.984 0.964 0.927 0.964 0.926

Appendix Table C-21. BTEX removal data from Column 10A during first sparging cycle.

Sample

Pore Volumes

Benzene Conc. (mg/L)

Benzene Mass Removed (mg)

TolueneConc. (mg/L)

Toluene Mass Removed(mg)

Ethyl-benzeneConc. (mg/L)

Ethyl-benzene Mass Removed(mg)

p-&m- xylene Conc. (mg/L)

p-&m-xylene Mass Removed(mg)

o- xylene Conc. (mg/L)

o-xylene Mass Removed(mg)

1 14.2 2.894 0.134 4.937 0.228 2.307 0.106 1.397 0.064 0.482 0.022 2 44.3 2.088 0.376 4.631 0.693 2.298 0.330 1.415 0.201 0.493 0.070 3 75.1 1.357 0.548 3.798 1.115 1.983 0.545 1.232 0.334 0.436 0.116 4 111.1 0.919 0.681 3.534 1.542 1.990 0.776 1.256 0.479 0.457 0.168 5 142.0 0.525 0.753 2.877 1.863 1.707 0.961 1.080 0.596 0.398 0.211 6 207.4 0.244 0.834 2.643 2.448 1.747 1.327 1.116 0.828 0.418 0.297 7 242.1 0.170 0.858 2.301 2.726 1.727 1.522 1.123 0.954 0.423 0.345 8 276.8 0.152 0.876 1.813 2.957 1.680 1.714 1.114 1.080 0.426 0.392 9 346.3 0.133 0.908 1.324 3.310 1.632 2.086 1.105 1.330 0.429 0.489 10 381.0 0.063 0.919 0.838 3.432 1.236 2.248 0.847 1.439 0.337 0.532 11 496.7 0.041 0.938 0.427 3.669 1.020 2.671 0.766 1.742 0.329 0.657 12 612.5 0.039 0.953 0.332 3.811 0.946 3.039 0.800 2.035 0.392 0.792 13 728.2 0.018 0.964 0.147 3.901 0.402 3.292 0.376 2.256 0.216 0.906 14 1075.4 0.009 0.979 0.064 4.020 0.114 3.582 0.111 2.530 0.084 1.075 15 1422.6 0.005 0.987 0.033 4.074 0.053 3.676 0.045 2.617 0.033 1.141 16 1793.0 0.006 0.993 0.045 4.121 0.068 3.749 0.057 2.678 0.036 1.182 17 2163.4 0.008 1.002 0.026 4.163 0.038 3.813 0.029 2.729 0.017 1.214 18 2533.8 0.002 1.008 0.016 4.189 0.022 3.848 0.017 2.757 0.009 1.229 19 2916.9 0.003 1.011 0.019 4.210 0.026 3.878 0.019 2.779 0.010 1.242 20 3044.6 0.002 1.012 0.019 4.218 0.028 3.889 0.019 2.787 0.012 1.246

109

Appendix Table C-22. BTEX removal data from Column 10A during second sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 17.9 2.116 0.123 3.639 0.211 1.638 0.095 1.174 0.068 1.555 0.090 2 62.6 1.531 0.387 3.821 0.752 1.752 0.341 1.261 0.245 1.662 0.323 3 100.9 1.260 0.560 4.267 1.254 1.972 0.572 1.446 0.413 1.897 0.544 4 142.4 0.523 0.680 2.708 1.723 1.328 0.794 0.987 0.576 1.293 0.759 5 213.4 0.287 0.773 2.984 2.377 1.782 1.151 1.379 0.848 1.862 1.122 6 250.5 0.164 0.800 2.121 2.683 1.496 1.348 1.185 1.002 1.637 1.331 7 287.5 0.134 0.818 1.809 2.919 1.365 1.520 1.084 1.138 1.486 1.519 8 338.6 0.101 0.838 1.369 3.182 1.297 1.740 1.057 1.315 1.458 1.762 9 383.3 0.085 0.851 1.062 3.358 1.253 1.925 1.050 1.468 1.473 1.975 10 466.3 0.070 0.872 0.687 3.594 1.147 2.247 1.025 1.747 1.511 2.376 11 517.4 0.057 0.882 0.507 3.692 0.993 2.424 0.937 1.910 1.427 2.619 12 594.0 0.046 0.895 0.361 3.800 0.786 2.645 0.801 2.125 1.345 2.963 13 638.7 0.040 0.901 0.291 3.847 0.631 2.748 0.672 2.232 1.198 3.147 14 906.9 0.024 0.929 0.153 4.041 0.247 3.130 0.301 2.655 0.748 3.993 15 1239.0 0.016 0.951 0.102 4.178 0.134 3.334 0.145 2.895 0.377 4.598 16 1649.0 0.012 0.970 0.081 4.299 0.102 3.490 0.100 3.057 0.220 4.995 17 2118.6 0.006 0.984 0.041 4.393 0.048 3.605 0.046 3.168 0.091 5.232 18 2575.0 0.005 0.993 0.036 4.450 0.040 3.670 0.036 3.229 0.069 5.350 19 2965.9 0.003 0.998 0.013 4.481 0.028 3.713 0.026 3.269 0.050 5.426 20 3281.4 0.003 1.002 0.022 4.500 0.027 3.741 0.024 3.295 0.045 5.474

110

Appendix Table C-23. BTEX removal data from Column 10A during third sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 9.6 3.139 0.097 4.828 0.150 2.482 0.077 1.561 0.048 2.229 0.069 2 47.9 1.922 0.412 4.163 0.708 2.236 0.370 1.417 0.233 2.012 0.332 3 84.9 1.269 0.603 3.536 1.170 1.959 0.622 1.236 0.392 1.778 0.560 4 122.0 0.818 0.728 3.579 1.597 2.145 0.868 1.375 0.549 2.023 0.788 5 159.0 0.553 0.810 3.839 2.042 2.570 1.151 1.664 0.731 2.502 1.059 6 197.3 0.193 0.857 1.871 2.396 1.308 1.391 0.842 0.887 1.264 1.293 7 277.6 0.076 0.892 1.161 2.791 1.262 1.726 0.858 1.108 1.410 1.641 8 314.6 0.103 0.903 1.530 2.952 1.870 1.914 1.266 1.236 2.049 1.848 9 388.7 0.034 0.919 0.463 3.191 0.813 2.235 0.568 1.456 0.951 2.208 10 512.1 0.040 0.934 0.379 3.360 0.944 2.587 0.706 1.710 1.250 2.649 11 639.8 0.037 0.950 0.229 3.485 0.674 2.922 0.577 1.976 1.219 3.160 12 742.0 0.034 0.961 0.226 3.561 0.604 3.133 0.556 2.163 1.282 3.574 13 1165.3 0.018 0.997 0.117 3.795 0.212 3.693 0.202 2.683 0.647 4.896 14 1548.9 0.013 1.016 0.077 3.916 0.109 3.893 0.093 2.867 0.249 5.453 15 1946.7 0.008 1.030 0.048 3.997 0.069 4.007 0.056 2.962 0.137 5.702 16 2391.1 0.008 1.041 0.050 4.068 0.078 4.113 0.064 3.049 0.154 5.912 17 2854.1 0.004 1.050 0.027 4.126 0.039 4.201 0.031 3.121 0.070 6.081 18 3347.9 0.009 1.061 0.028 4.171 0.039 4.263 0.031 3.170 0.072 6.194 19 3394.2 0.006 1.062 0.032 4.175 0.043 4.270 0.034 3.175 0.073 6.205

111

Appendix Table C-24. BTEX removal data from Column 10A during fourth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 10.9 3.048 0.108 5.519 0.195 3.098 0.109 2.109 0.074 2.705 0.095 2 49.7 1.725 0.408 4.683 0.836 3.043 0.496 2.126 0.341 2.819 0.443 3 89.8 1.551 0.621 5.197 1.479 3.277 0.906 2.269 0.626 3.029 0.823 4 133.1 0.866 0.790 4.648 2.168 3.081 1.351 2.137 0.935 2.848 1.234 5 219.5 0.266 0.948 3.274 3.277 2.813 2.177 1.983 1.512 2.711 2.013 6 264.2 0.206 0.983 2.873 3.722 2.824 2.585 1.994 1.800 2.714 2.406 7 308.9 0.152 1.009 2.150 4.086 2.600 2.978 1.877 2.080 2.598 2.790 8 391.9 0.099 1.042 1.280 4.547 2.240 3.628 1.716 2.563 2.525 3.479 9 462.1 0.075 1.062 0.865 4.791 1.986 4.109 1.591 2.939 2.442 4.044 10 577.1 0.068 1.089 0.606 5.065 1.716 4.799 1.520 3.519 2.659 4.994 11 698.4 0.048 1.111 0.372 5.257 1.074 5.347 1.047 4.023 2.090 5.928 12 804.2 0.039 1.126 0.278 5.369 0.736 5.657 0.773 4.336 1.761 6.588 13 1201.0 0.025 1.168 0.172 5.658 0.308 6.328 0.320 5.038 0.867 8.278 14 1545.0 0.017 1.191 0.121 5.822 0.195 6.608 0.185 5.319 0.450 9.012 15 2011.4 0.013 1.214 0.086 5.978 0.130 6.854 0.118 5.548 0.254 9.544 16 2346.1 0.009 1.226 0.058 6.057 0.086 6.971 0.077 5.653 0.161 9.769 17 2778.2 0.008 1.238 0.054 6.135 0.078 7.085 0.069 5.756 0.137 9.977 18 3302.9 0.007 1.250 0.041 6.215 0.057 7.199 0.050 5.857 0.098 10.177 19 3850.4 0.005 1.261 0.036 6.283 0.050 7.293 0.045 5.940 0.083 10.337

112

Appendix Table C-25. BTEX removal data from Column 10A during fifth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 14.7 3.030 0.145 5.959 0.284 3.070 0.147 2.318 0.111 2.993 0.143 2 42.5 2.286 0.384 5.632 0.806 3.055 0.422 2.365 0.321 3.152 0.419 3 79.5 1.591 0.616 5.444 1.471 3.139 0.794 2.478 0.612 3.350 0.810 4 119.7 1.023 0.786 5.309 2.170 3.213 1.207 2.539 0.938 3.469 1.253 5 206.1 0.350 0.979 4.115 3.489 3.008 2.078 2.402 1.630 3.302 2.201 6 249.3 0.235 1.020 3.286 4.007 2.814 2.485 2.262 1.956 3.121 2.650 7 304.9 0.164 1.055 2.196 4.500 2.411 2.955 1.993 2.339 2.828 3.186 8 400.6 0.112 1.098 1.435 5.064 2.348 3.694 2.037 2.965 2.966 4.085 9 496.4 0.083 1.129 0.885 5.424 1.913 4.355 1.778 3.557 2.802 4.980 10 643.3 0.060 1.162 0.528 5.760 1.328 5.126 1.410 4.316 2.613 6.268 11 764.6 0.055 1.185 0.446 5.951 1.077 5.599 1.244 4.837 2.700 7.312 12 1013.7 0.034 1.221 0.255 6.234 0.461 6.219 0.564 5.567 1.490 9.002 13 1384.0 0.022 1.255 0.158 6.482 0.220 6.628 0.241 6.050 0.638 10.279 14 1780.9 0.016 1.280 0.116 6.657 0.147 6.864 0.152 6.302 0.353 10.916 15 2233.5 0.011 1.300 0.081 6.802 0.101 7.046 0.101 6.488 0.215 11.332 16 2645.8 0.009 1.313 0.066 6.900 0.080 7.167 0.079 6.608 0.161 11.583 17 3101.7 0.008 1.326 0.056 6.991 0.069 7.277 0.068 6.717 0.132 11.800 18 3728.5 0.006 1.340 0.047 7.096 0.057 7.405 0.055 6.842 0.107 12.042

113

Appendix Table C-26. BTEX removal data from Column 10A during sixth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 10.6 2.566 0.088 4.908 0.168 2.379 0.082 1.779 0.061 2.017 0.069 2 61.4 1.949 0.460 5.602 1.034 3.021 0.526 2.423 0.407 3.023 0.484 3 120.7 0.995 0.742 4.931 2.045 2.835 1.088 2.289 0.860 2.886 1.051 4 172.5 0.506 0.869 4.079 2.802 2.630 1.548 2.141 1.232 2.694 1.520 5 285.9 0.192 0.997 2.403 3.992 2.494 2.489 2.142 2.018 2.741 2.518 6 346.4 0.141 1.029 1.727 4.397 2.197 2.948 1.949 2.419 2.543 3.036 7 406.8 0.113 1.054 1.282 4.692 2.001 3.359 1.860 2.792 2.544 3.534 8 527.8 0.080 1.092 0.741 5.088 1.505 4.046 1.550 3.460 2.403 4.504 9 626.0 0.065 1.115 0.537 5.292 1.148 4.469 1.279 3.910 2.192 5.235 10 762.1 0.051 1.141 0.379 5.494 0.766 4.891 0.915 4.394 1.795 6.114 11 877.8 0.042 1.158 0.296 5.620 0.531 5.134 0.650 4.687 1.387 6.710 12 1541.4 0.022 1.227 0.143 6.093 0.170 5.887 0.189 5.590 0.396 8.627 13 1904.1 0.016 1.249 0.107 6.240 0.117 6.056 0.123 5.773 0.233 8.996 14 2367.0 0.012 1.270 0.081 6.381 0.087 6.210 0.089 5.932 0.161 9.291 15 2914.5 0.009 1.289 0.062 6.508 0.067 6.347 0.068 6.071 0.118 9.539 16 3333.2 0.008 1.300 0.054 6.586 0.059 6.433 0.059 6.157 0.102 9.688 17 3776.1 0.007 1.310 0.047 6.658 0.051 6.511 0.052 6.237 0.087 9.823

114

Appendix Table C-27. BTEX removal data from Column 10A during seventh sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 11.6 2.742 0.103 5.271 0.198 2.615 0.098 1.678 0.063 1.913 0.072 2 59.5 1.965 0.468 5.238 1.013 2.980 0.532 1.982 0.347 2.614 0.423 3 110.6 1.124 0.724 5.070 1.866 3.160 1.040 2.192 0.692 3.060 0.893 4 158.4 0.615 0.859 4.402 2.601 2.978 1.517 2.086 1.024 2.946 1.359 5 360.5 0.137 1.105 1.610 4.569 2.208 3.214 1.721 2.270 2.568 3.163 6 403.7 0.143 1.124 1.453 4.783 2.211 3.523 1.772 2.515 2.725 3.534 7 455.1 0.112 1.145 1.154 5.000 2.193 3.890 1.881 2.819 3.020 4.012 8 595.7 0.078 1.189 0.688 5.420 1.521 4.736 1.432 3.574 2.694 5.314 9 728.5 0.059 1.218 0.474 5.669 1.073 5.294 1.080 4.114 2.311 6.391 10 861.3 0.046 1.241 0.352 5.847 0.754 5.687 0.787 4.516 1.846 7.285 11 1245.6 0.031 1.289 0.216 6.201 0.347 6.372 0.353 5.226 0.909 9.000 12 1765.6 0.017 1.330 0.116 6.481 0.171 6.809 0.150 5.649 0.382 10.088 13 2252.1 0.013 1.353 0.093 6.646 0.146 7.058 0.112 5.856 0.300 10.625 14 2767.7 0.010 1.372 0.072 6.784 0.093 7.258 0.087 6.022 0.174 11.021 15 3212.2 0.008 1.385 0.059 6.878 0.077 7.380 0.072 6.136 0.142 11.249 16 3671.4 0.006 1.395 0.050 6.959 0.064 7.486 0.061 6.235 0.115 11.440

115

Appendix Table C-28. BTEX removal data from Column 10A during eighth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 12.8 2.207 0.091 4.568 0.189 2.529 0.105 1.869 0.077 2.494 0.103 2 67.2 1.569 0.425 4.768 1.013 2.858 0.580 2.194 0.436 3.139 0.600 3 122.8 0.807 0.638 4.123 1.813 2.546 1.066 1.955 0.809 2.799 1.135 4 182.1 0.353 0.750 3.064 2.503 2.130 1.515 1.649 1.155 2.373 1.631 5 293.2 0.155 0.841 1.976 3.410 2.107 2.278 1.719 1.761 2.519 2.512 6 352.4 0.120 0.868 1.439 3.738 1.927 2.665 1.631 2.083 2.434 2.987 7 404.3 0.100 0.886 1.076 3.949 1.755 2.974 1.545 2.350 2.397 3.393 8 552.4 0.072 0.927 0.600 4.351 1.281 3.703 1.287 3.029 2.272 4.513 9 663.5 0.055 0.950 0.412 4.533 0.906 4.097 0.985 3.438 2.015 5.285 10 774.6 0.033 0.966 0.240 4.651 0.511 4.352 0.592 3.722 1.362 5.893 11 885.8 0.037 0.979 0.256 4.740 0.475 4.529 0.563 3.930 1.390 6.388 12 1345.0 0.022 1.023 0.149 5.042 0.205 5.035 0.222 4.513 0.566 7.844 13 1777.1 0.016 1.050 0.105 5.220 0.130 5.269 0.133 4.762 0.300 8.450 14 2289.3 0.011 1.073 0.077 5.371 0.092 5.453 0.091 4.948 0.191 8.857 15 2716.1 0.008 1.087 0.057 5.464 0.071 5.566 0.064 5.055 0.137 9.083 16 3328.0 0.007 1.102 0.049 5.570 0.060 5.696 0.059 5.177 0.119 9.336 17 3521.2 0.006 1.106 0.046 5.599 0.056 5.732 0.055 5.212 0.108 9.407

116

Appendix Table C-29. BTEX removal data from Column 10A during ninth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 16.5 2.283 0.122 4.893 0.262 2.458 0.132 1.860 0.100 2.407 0.129 2 70.0 1.489 0.449 4.428 1.069 2.328 0.546 1.771 0.414 2.320 0.538 3 123.4 0.682 0.637 3.404 1.746 1.933 0.915 1.506 0.698 2.082 0.919 4 177.8 0.405 0.733 3.663 2.370 2.593 1.314 2.088 1.015 2.926 1.361 5 288.9 0.156 0.833 1.892 3.370 1.864 2.116 1.526 1.665 2.137 2.272 6 340.8 0.120 0.857 1.410 3.647 1.693 2.415 1.427 1.913 2.021 2.621 7 392.7 0.102 0.875 1.097 3.858 1.590 2.691 1.389 2.150 2.051 2.963 8 570.4 0.061 0.922 0.488 4.314 0.968 3.428 0.981 2.832 1.722 4.050 9 714.9 0.046 0.947 0.329 4.505 0.613 3.798 0.684 3.222 1.391 4.779 10 800.1 0.040 0.959 0.278 4.589 0.499 3.951 0.571 3.395 1.279 5.147 11 926.0 0.034 0.974 0.231 4.693 0.370 4.128 0.433 3.600 1.053 5.623 12 1402.2 0.021 1.017 0.140 4.979 0.171 4.545 0.183 4.076 0.429 6.766 13 2027.2 0.013 1.051 0.087 5.208 0.097 4.817 0.099 4.360 0.201 7.405 14 2523.6 0.009 1.069 0.065 5.331 0.072 4.953 0.072 4.497 0.138 7.678 15 2950.4 0.008 1.081 0.055 5.414 0.061 5.046 0.060 4.588 0.114 7.852 16 3457.6 0.006 1.092 0.044 5.496 0.050 5.137 0.049 4.679 0.091 8.021 17 3658.9 0.005 1.095 0.040 5.523 0.045 5.168 0.044 4.709 0.081 8.077

117

Appendix Table C-30. BTEX removal data from Column 10A during tenth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 14.7 1.582 0.075 3.413 0.163 1.656 0.079 1.294 0.062 1.460 0.070 2 57.7 1.299 0.276 3.665 0.655 1.852 0.323 1.491 0.256 1.760 0.294 3 113.9 0.786 0.466 3.634 1.320 1.875 0.663 1.506 0.528 1.778 0.616 4 164.4 0.382 0.562 3.011 1.864 1.762 0.960 1.434 0.769 1.708 0.901 5 255.3 0.147 0.639 1.774 2.568 1.458 1.434 1.229 1.161 1.510 1.375 6 303.6 0.104 0.659 1.292 2.808 1.318 1.652 1.148 1.347 1.427 1.605 7 355.4 0.079 0.675 0.913 2.993 1.168 1.860 1.048 1.532 1.356 1.838 8 540.6 0.056 0.715 0.468 3.408 0.857 2.468 0.887 2.112 1.371 2.657 9 652.4 0.038 0.732 0.292 3.545 0.561 2.725 0.634 2.388 1.110 3.106 10 785.2 0.032 0.747 0.223 3.656 0.373 2.926 0.438 2.618 0.862 3.530 11 987.9 0.030 0.767 0.208 3.798 0.312 3.150 0.387 2.890 0.859 4.095 12 1441.8 0.015 0.801 0.109 4.030 0.132 3.477 0.144 3.280 0.303 4.950 13 1901.1 0.014 0.823 0.089 4.178 0.098 3.649 0.101 3.462 0.194 5.320 14 2628.3 0.009 0.849 0.062 4.356 0.070 3.847 0.069 3.663 0.127 5.698 15 3106.7 0.005 0.860 0.040 4.435 0.045 3.936 0.045 3.751 0.078 5.857 16 3353.6 0.006 0.864 0.044 4.468 0.049 3.973 0.049 3.788 0.085 5.922

118

Appendix Table C-31. BTEX removal data from Column 10B during first sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 11.3 3.204 0.124 5.655 0.219 2.888 0.112 1.816 0.070 0.657 0.025 2 44.1 2.241 0.430 5.108 0.824 2.593 0.420 1.606 0.263 0.557 0.094 3 72.3 1.578 0.615 4.598 1.294 2.453 0.664 1.533 0.415 0.536 0.147 4 106.2 1.000 0.765 4.264 1.808 2.402 0.946 1.518 0.592 0.542 0.209 5 140.0 0.595 0.857 3.780 2.276 2.343 1.222 1.483 0.766 0.538 0.272 6 173.9 0.342 0.912 3.069 2.673 2.063 1.477 1.305 0.928 0.476 0.331 7 219.0 0.189 0.953 2.312 3.090 1.860 1.781 1.193 1.121 0.442 0.402 8 271.5 0.115 0.980 1.721 3.453 1.788 2.110 1.181 1.335 0.448 0.482 9 329.8 0.077 0.999 1.174 3.742 1.588 2.447 1.086 1.562 0.430 0.570 10 546.9 0.026 1.038 0.304 4.293 0.726 3.309 0.604 2.191 0.304 0.843 11 686.9 0.017 1.048 0.262 4.429 0.492 3.601 0.428 2.438 0.241 0.974 12 791.8 0.013 1.054 0.165 4.506 0.400 3.762 0.366 2.581 0.226 1.058 13 1141.7 0.008 1.066 0.064 4.643 0.134 4.082 0.126 2.876 0.085 1.244 14 1491.6 0.004 1.074 0.027 4.698 0.048 4.192 0.043 2.977 0.028 1.312 15 1853.5 0.003 1.078 0.012 4.722 0.018 4.233 0.015 3.013 0.010 1.336 16 2215.4 0.002 1.082 0.022 4.743 0.036 4.267 0.028 3.040 0.016 1.352 17 2577.3 0.002 1.085 0.020 4.769 0.039 4.313 0.030 3.076 0.017 1.373 18 2966.0 0.002 1.087 0.014 4.792 0.026 4.357 0.019 3.109 0.010 1.391 19 3056.7 0.002 1.088 0.013 4.796 0.025 4.365 0.018 3.115 0.010 1.394

119

Appendix Table C-32. BTEX removal data from Column 10B during second sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 52.5 1.316 0.237 3.080 0.554 1.561 0.281 1.084 0.195 1.489 0.268 2 91.4 1.399 0.418 4.511 1.061 2.341 0.541 1.633 0.376 2.229 0.516 3 126.3 0.685 0.543 3.154 1.520 1.757 0.787 1.250 0.549 1.730 0.753 4 161.3 0.130 0.592 0.850 1.761 0.508 0.923 0.366 0.646 0.513 0.888 5 196.3 0.173 0.610 1.520 1.903 1.076 1.018 0.799 0.716 1.152 0.988 6 231.3 0.083 0.626 0.946 2.051 0.809 1.131 0.626 0.801 0.931 1.113 7 266.3 0.029 0.632 0.388 2.131 0.410 1.204 0.330 0.859 0.510 1.199 8 301.3 0.055 0.637 0.740 2.198 0.794 1.276 0.636 0.917 0.956 1.287 9 336.2 0.045 0.643 0.612 2.280 0.731 1.368 0.600 0.991 0.923 1.400 10 382.9 0.064 0.652 0.809 2.393 1.075 1.512 0.896 1.111 1.408 1.587 11 560.8 0.050 0.687 0.498 2.792 0.914 2.120 0.860 1.646 1.556 2.491 12 802.1 0.026 0.718 0.201 3.081 0.390 2.659 0.403 2.169 0.867 3.494 13 922.8 0.020 0.728 0.151 3.154 0.275 2.797 0.288 2.312 0.660 3.809 14 1296.7 0.012 0.748 0.087 3.307 0.133 3.059 0.134 2.582 0.320 4.438 15 1610.4 0.011 0.761 0.076 3.394 0.111 3.190 0.105 2.710 0.238 4.738 16 1991.5 0.008 0.774 0.059 3.482 0.079 3.313 0.071 2.825 0.152 4.992 17 2435.1 0.005 0.783 0.036 3.554 0.052 3.413 0.045 2.914 0.092 5.178 18 2872.4 0.004 0.789 0.023 3.599 0.037 3.479 0.033 2.972 0.066 5.297 19 3116.0 0.003 0.792 0.021 3.618 0.033 3.509 0.029 2.998 0.057 5.348

120

Appendix Table C-33. BTEX removal data from Column 10B during third sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 12.2 2.588 0.109 3.839 0.161 1.940 0.081 1.195 0.050 1.710 0.072 2 50.4 2.235 0.424 5.190 0.752 2.761 0.389 1.700 0.240 2.413 0.342 3 85.4 1.484 0.648 5.131 1.372 2.784 0.722 1.704 0.444 2.412 0.631 4 120.4 0.710 0.779 4.082 1.924 2.528 1.040 1.569 0.640 2.280 0.913 5 155.4 0.346 0.843 2.931 2.345 2.074 1.317 1.311 0.813 1.946 1.166 6 190.4 0.247 0.878 2.648 2.680 2.221 1.574 1.433 0.978 2.166 1.413 7 231.2 0.167 0.907 2.011 3.006 1.992 1.869 1.308 1.170 2.016 1.706 8 272.0 0.119 0.927 1.383 3.244 1.656 2.124 1.118 1.339 1.775 1.971 9 312.8 0.105 0.943 1.281 3.430 1.981 2.379 1.405 1.516 2.382 2.262 10 350.7 0.071 0.954 0.771 3.563 1.294 2.592 0.940 1.668 1.608 2.521 11 601.4 0.024 0.995 0.190 3.976 0.438 3.337 0.397 2.243 0.951 3.622 12 718.0 0.019 1.004 0.155 4.046 0.396 3.503 0.389 2.400 1.086 4.030 13 1044.6 0.020 1.025 0.102 4.190 0.165 3.817 0.150 2.703 0.408 4.867 14 1417.8 0.047 1.069 0.131 4.339 0.196 4.048 0.164 2.904 0.395 5.381 15 1767.6 0.018 1.108 0.063 4.456 0.092 4.221 0.076 3.048 0.173 5.722 16 2094.1 0.010 1.123 0.049 4.519 0.062 4.307 0.049 3.118 0.107 5.879 17 2444.0 0.008 1.133 0.042 4.573 0.056 4.378 0.045 3.174 0.100 6.003 18 2825.1 0.006 1.143 0.035 4.623 0.047 4.445 0.036 3.227 0.078 6.119 19 3233.3 0.004 1.150 0.024 4.665 0.033 4.501 0.026 3.270 0.055 6.212

121

Appendix Table C-34. BTEX removal data from Column 10B during fourth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 10.9 3.108 0.117 5.645 0.212 3.148 0.118 2.176 0.082 2.710 0.102 2 53.2 1.733 0.467 4.855 0.972 2.909 0.557 1.976 0.382 2.566 0.484 3 113.5 0.614 0.710 4.315 1.921 3.075 1.176 2.130 0.807 2.810 1.040 4 151.0 0.370 0.773 3.883 2.448 3.280 1.584 2.304 1.092 3.114 1.421 5 188.4 0.237 0.812 3.060 2.894 3.105 1.995 2.229 1.383 3.087 1.819 6 225.9 0.165 0.838 2.230 3.234 2.726 2.370 2.004 1.656 2.817 2.199 7 269.7 0.127 0.860 1.608 3.522 2.510 2.762 1.907 1.949 2.818 2.621 8 313.4 0.098 0.877 1.135 3.728 2.222 3.117 1.764 2.224 2.724 3.037 9 365.2 0.081 0.893 0.801 3.900 1.895 3.483 1.581 2.522 2.607 3.511 10 598.5 0.048 0.944 0.333 4.354 0.827 4.572 0.833 3.487 1.812 5.279 11 773.4 0.035 0.969 0.225 4.521 0.456 4.957 0.473 3.879 1.176 6.175 12 941.8 0.030 0.988 0.176 4.637 0.293 5.173 0.294 4.100 0.746 6.730 13 1175.1 0.026 1.011 0.141 4.764 0.202 5.372 0.189 4.294 0.445 7.206 14 1531.4 0.020 1.039 0.111 4.919 0.146 5.584 0.128 4.487 0.262 7.638 15 1894.2 0.016 1.061 0.094 5.046 0.119 5.749 0.102 4.631 0.198 7.925 16 2318.1 0.013 1.082 0.089 5.180 0.115 5.919 0.098 4.776 0.181 8.200 17 2674.7 0.010 1.096 0.077 5.281 0.108 6.056 0.090 4.891 0.163 8.410 18 3165.8 0.009 1.113 0.054 5.391 0.084 6.217 0.072 5.027 0.129 8.656 19 3536.6 0.011 1.126 0.055 5.460 0.081 6.323 0.071 5.118 0.132 8.822

122

Appendix Table C-35. BTEX removal data from Column 10B during fifth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 6.7 3.058 0.071 5.068 0.117 2.297 0.053 1.852 0.043 1.985 0.046 2 40.6 2.195 0.376 5.787 0.747 3.051 0.364 2.441 0.292 3.177 0.346 3 78.1 1.403 0.607 5.176 1.452 2.818 0.741 2.179 0.589 2.964 0.740 4 118.7 0.772 0.758 4.561 2.130 2.729 1.127 2.131 0.889 2.933 1.151 5 156.2 0.427 0.835 3.625 2.656 2.401 1.457 1.881 1.147 2.619 1.508 6 199.9 0.254 0.886 3.089 3.160 2.441 1.820 1.949 1.434 2.764 1.912 7 245.2 0.169 0.919 2.389 3.586 2.280 2.187 1.861 1.731 2.701 2.337 8 284.1 0.126 0.939 1.839 3.868 2.071 2.477 1.725 1.970 2.554 2.687 9 342.4 0.092 0.961 1.256 4.177 1.817 2.866 1.572 2.299 2.453 3.188 10 387.8 0.078 0.974 0.968 4.350 1.621 3.133 1.456 2.535 2.363 3.562 11 601.6 0.049 1.021 0.444 4.868 1.066 4.119 1.150 3.491 2.342 5.288 12 802.4 0.034 1.049 0.224 5.098 0.475 4.649 0.556 4.078 1.308 6.545 13 1058.1 0.021 1.074 0.157 5.265 0.274 4.978 0.315 4.460 0.806 7.472 14 1414.7 0.015 1.096 0.105 5.425 0.148 5.236 0.158 4.749 0.381 8.198 15 1859.3 0.011 1.116 0.077 5.564 0.102 5.426 0.105 4.949 0.224 8.659 16 2296.6 0.011 1.133 0.065 5.670 0.077 5.561 0.077 5.085 0.152 8.941 17 2806.2 0.010 1.151 0.061 5.780 0.071 5.690 0.068 5.212 0.125 9.183 18 3275.3 0.010 1.168 0.052 5.870 0.057 5.793 0.056 5.312 0.106 9.370 19 3796.0 0.009 1.185 0.050 5.961 0.052 5.890 0.051 5.408 0.091 9.546

123

Appendix Table C-36. BTEX removal data from Column 10B during sixth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 17.5 2.727 0.164 5.156 0.309 2.642 0.159 2.292 0.138 2.357 0.141 2 59.6 1.455 0.466 5.078 1.048 2.889 0.558 2.300 0.469 2.891 0.521 3 103.3 0.646 0.623 3.886 1.721 2.560 0.967 2.073 0.797 2.652 0.936 4 155.8 0.289 0.707 2.842 2.326 2.348 1.408 1.976 1.162 2.612 1.410 5 204.8 0.171 0.746 2.031 2.736 2.036 1.776 1.739 1.474 2.408 1.832 6 253.8 0.115 0.770 1.440 3.027 1.755 2.095 1.549 1.750 2.243 2.223 7 310.9 0.085 0.790 1.006 3.267 1.491 2.413 1.371 2.036 2.104 2.648 8 368.0 0.066 0.804 0.727 3.437 1.262 2.683 1.214 2.289 1.952 3.046 9 619.9 0.035 0.848 0.281 3.872 0.556 3.468 0.616 3.080 1.217 4.415 10 848.4 0.023 0.871 0.177 4.052 0.319 3.811 0.366 3.465 0.776 5.196 11 1190.9 0.016 0.894 0.107 4.218 0.162 4.094 0.184 3.788 0.389 5.881 12 1810.5 0.013 0.924 0.074 4.411 0.090 4.362 0.100 4.089 0.174 6.479 13 2167.8 0.009 0.938 0.055 4.490 0.065 4.458 0.068 4.191 0.119 6.659 14 2614.4 0.009 0.952 0.049 4.570 0.054 4.549 0.058 4.288 0.095 6.823 15 3131.6 0.009 0.968 0.045 4.653 0.046 4.638 0.047 4.381 0.076 6.975 16 3527.1 0.010 0.981 0.048 4.717 0.045 4.700 0.043 4.442 0.070 7.074

124

Appendix Table C-37. BTEX removal data from Column 10B during seventh sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 15.9 2.475 0.135 5.773 0.315 3.272 0.178 2.503 0.137 3.118 0.170 2 73.1 0.931 0.469 4.720 1.344 3.130 0.806 2.275 0.605 3.074 0.777 3 124.5 0.379 0.585 3.340 2.055 2.807 1.330 2.110 0.992 2.948 1.309 4 176.0 0.192 0.635 2.202 2.544 2.476 1.796 1.942 1.350 2.833 1.819 5 232.0 0.126 0.666 1.409 2.891 2.090 2.235 1.730 1.702 2.694 2.349 6 287.9 0.092 0.687 0.924 3.115 1.678 2.596 1.476 2.010 2.448 2.843 7 340.4 0.074 0.701 0.652 3.257 1.358 2.870 1.250 2.255 2.234 3.264 8 399.9 0.061 0.715 0.477 3.372 1.047 3.115 1.017 2.486 1.956 3.692 9 704.3 0.034 0.765 0.224 3.738 0.369 3.854 0.394 3.223 0.920 5.193 10 945.7 0.028 0.790 0.174 3.902 0.258 4.113 0.272 3.498 0.650 5.843 11 1365.5 0.017 0.822 0.100 4.100 0.131 4.393 0.119 3.780 0.271 6.506 12 1743.3 0.013 0.842 0.078 4.214 0.095 4.540 0.082 3.910 0.176 6.796 13 2282.7 0.011 0.864 0.067 4.348 0.086 4.707 0.067 4.048 0.147 7.095 14 2765.5 0.007 0.878 0.042 4.438 0.084 4.848 0.047 4.143 0.192 7.375 15 3248.3 0.008 0.891 0.048 4.512 0.055 4.963 0.049 4.223 0.087 7.606 16 3549.2 0.009 0.900 0.052 4.563 0.065 5.025 0.061 4.280 0.107 7.706

125

Appendix Table C-38. BTEX removal data from Column 10B during eighth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 21.0 1.893 0.136 4.754 0.342 2.643 0.190 2.020 0.145 2.783 0.200 2 70.0 0.726 0.356 3.804 1.061 2.602 0.631 2.087 0.490 3.131 0.697 3 122.4 0.294 0.448 2.764 1.652 2.449 1.085 2.007 0.859 2.960 1.245 4 167.9 0.171 0.484 1.933 2.019 2.195 1.448 1.861 1.161 2.893 1.702 5 223.9 0.100 0.511 1.095 2.309 1.655 1.817 1.492 1.482 2.489 2.219 6 281.0 0.073 0.527 0.720 2.487 1.343 2.111 1.289 1.755 2.319 2.690 7 331.0 0.058 0.539 0.505 2.592 1.046 2.316 1.055 1.956 2.040 3.063 8 388.1 0.055 0.550 0.435 2.684 0.938 2.510 0.996 2.157 2.137 3.472 9 666.6 0.027 0.589 0.171 2.974 0.271 3.087 0.298 2.775 0.728 4.840 10 873.6 0.020 0.605 0.127 3.080 0.179 3.247 0.195 2.950 0.457 5.261 11 1237.8 0.014 0.627 0.085 3.213 0.107 3.425 0.110 3.141 0.236 5.694 12 1673.3 0.011 0.645 0.062 3.322 0.071 3.558 0.071 3.276 0.138 5.974 13 2066.0 0.009 0.658 0.054 3.400 0.063 3.648 0.062 3.366 0.111 6.142 14 2547.0 0.009 0.672 0.044 3.482 0.052 3.743 0.052 3.461 0.101 6.316 15 2940.6 0.007 0.683 0.035 3.536 0.040 3.805 0.036 3.521 0.071 6.432 16 3487.3 0.008 0.696 0.037 3.603 0.043 3.883 0.042 3.594 0.085 6.579

126

Appendix Table C-39. BTEX removal data from Column 10B during ninth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 14.6 2.052 0.103 4.756 0.238 2.358 0.118 1.953 0.098 2.282 0.114 2 58.3 0.867 0.321 3.670 0.870 2.153 0.456 1.673 0.370 2.162 0.447 3 106.9 0.334 0.422 2.382 1.374 1.812 0.787 1.487 0.633 2.007 0.795 4 158.7 0.174 0.467 1.778 1.744 2.055 1.130 1.831 0.928 2.884 1.230 5 211.5 0.108 0.492 1.037 1.999 1.289 1.433 1.153 1.198 1.840 1.657 6 254.4 0.083 0.506 0.743 2.130 1.053 1.606 0.985 1.356 1.655 1.914 7 310.6 0.064 0.520 0.526 2.252 0.862 1.790 0.850 1.532 1.527 2.221 8 360.1 0.053 0.530 0.392 2.330 0.671 1.920 0.681 1.662 1.291 2.460 9 626.1 0.030 0.568 0.179 2.590 0.267 2.348 0.294 2.107 0.640 3.341 10 824.6 0.022 0.586 0.124 2.693 0.149 2.490 0.160 2.262 0.346 3.677 11 1201.4 0.017 0.611 0.090 2.832 0.100 2.650 0.101 2.431 0.204 4.032 12 1633.5 0.012 0.633 0.066 2.948 0.071 2.777 0.074 2.561 0.126 4.277 13 2200.3 0.009 0.653 0.049 3.059 0.052 2.896 0.051 2.683 0.089 4.486 14 2634.1 0.008 0.666 0.045 3.129 0.046 2.968 0.045 2.754 0.077 4.610 15 3005.0 0.008 0.676 0.039 3.182 0.041 3.024 0.040 2.809 0.069 4.703 16 3445.8 0.007 0.687 0.036 3.239 0.034 3.080 0.033 2.864 0.057 4.799

127

Appendix Table C-40. BTEX removal data from Column 10B during tenth sparging cycle.

Sample

Pore Volumes



TolueneConc. (mg/L)








1 16.197 1.769 0.098 4.445 0.247 2.026 0.113 1.625 0.090 1.843 0.102 2 59.929 0.674 0.282 3.080 0.811 1.733 0.395 1.444 0.321 1.686 0.367 3 107.024 0.283 0.359 2.080 1.228 1.504 0.656 1.310 0.543 1.622 0.634 4 158.474 0.140 0.396 1.310 1.527 1.239 0.898 1.135 0.759 1.501 0.910 5 206.872 0.087 0.415 0.861 1.707 1.020 1.086 0.983 0.934 1.386 1.150 6 255.852 0.063 0.428 0.583 1.829 0.805 1.239 0.810 1.085 1.213 1.368 7 360.808 0.046 0.447 0.358 1.998 0.633 1.498 0.693 1.356 1.282 1.817 8 504.249 0.029 0.465 0.175 2.129 0.263 1.718 0.298 1.599 0.553 2.268 9 765.229 0.017 0.486 0.098 2.252 0.115 1.888 0.128 1.790 0.250 2.628 10 1043.684 0.015 0.501 0.077 2.335 0.079 1.980 0.082 1.890 0.153 2.821 11 1433.198 0.011 0.518 0.059 2.426 0.054 2.069 0.055 1.981 0.090 2.983 12 1965.898 0.008 0.535 0.047 2.523 0.049 2.164 0.049 2.076 0.081 3.139 13 2421.286 0.007 0.547 0.039 2.590 0.039 2.232 0.039 2.145 0.063 3.251 14 3079.070 0.006 0.561 0.031 2.669 0.039 2.320 0.033 2.227 0.071 3.402 15 3353.749 0.006 0.567 0.031 2.698 0.029 2.352 0.029 2.256 0.049 3.459

128

129

Appendix Table C-41. Kd, Mass sorbed, mass removed, and cumulative mass remaining for BTEX compounds on Column 10A.

Compound Kd (L/kg) Mass sorbed (mg) Mass removed (mg)

Cum. mass remaining (mg)

Benzene BTC 1 15.1 1.02 1.1 -0.08 Benzene BTC 2 20.8 1.45 1 0.37 Benzene BTC 3 20.2 1.65 1.06 0.96 Benzene BTC 4 16.4 1.09 1.26 0.79 Benzene BTC 5 16.4 1.12 1.34 0.57 Benzene BTC 6 17.6 1.19 1.31 0.45 Benzene BTC 7 11.3 0.78 1.4 -0.17 Benzene BTC 8 19.5 1.27 1.11 -0.01 Benzene BTC 9 14.5 0.97 1.1 -0.14

Benzene BTC 10 13.9 1.02 0.86 0.02 Toluene BTC 1 34.0 4.56 4.22 0.34 Toluene BTC 2 37.8 5.68 4.5 1.52 Toluene BTC 3 37.8 6.9 4.18 4.24 Toluene BTC 4 38.4 5.75 6.28 3.71 Toluene BTC 5 37.2 5.84 7.1 2.45 Toluene BTC 6 37.2 5.89 6.66 1.68 Toluene BTC 7 29.6 4.71 6.96 -0.57 Toluene BTC 8 41.6 6.23 5.6 0.06 Toluene BTC 9 32.1 5.04 5.52 -0.42

Toluene BTC 10 29.6 4.96 4.47 0.07 Ethylbenzene BTC 1 92.6 5.21 3.89 1.32 Ethylbenzene BTC 2 89.4 5.36 3.74 2.94 Ethylbenzene BTC 3 92.6 8.35 4.27 7.02 Ethylbenzene BTC 4 90.7 6.34 7.29 6.07 Ethylbenzene BTC 5 89.4 6.07 7.4 4.74 Ethylbenzene BTC 6 92.0 6.24 6.51 4.47 Ethylbenzene BTC 7 83.1 6.15 7.49 3.13 Ethylbenzene BTC 8 90.1 6.13 5.73 3.53 Ethylbenzene BTC 9 76.2 5.5 5.17 3.86 Ethylbenzene BTC 10 69.9 4.94 3.97 4.83 p-&m-xylene BTC 1 100.2 3.58 2.79 0.79 p-&m-xylene BTC 2 103.9 4.72 3.29 2.22 p-&m-xylene BTC 3 95.1 5.6 3.17 4.65 p-&m-xylene BTC 4 98.3 4.74 5.94 3.45 p-&m-xylene BTC 5 96.4 5.11 6.84 1.72 p-&m-xylene BTC 6 93.2 5.13 6.24 0.61 p-&m-xylene BTC 7 87.6 4.66 6.23 -0.96 p-&m-xylene BTC 8 98.3 5.22 5.21 -0.95 p-&m-xylene BTC 9 86.9 5.58 4.71 -0.08 p-&m-xylene BTC 10 76.2 4.47 3.79 0.6

o-xylene BTC 1 97.0 1.28 1.25 0.03 o-xylene BTC 2 93.9 6.61 5.47 1.17 o-xylene BTC 3 92.6 9.34 6.21 4.3 o-xylene BTC 4 88.8 6.66 10.34 0.62 o-xylene BTC 5 88.8 7.35 12.04 -4.07 o-xylene BTC 6 83.8 6.51 9.82 -7.38 o-xylene BTC 7 81.3 6.9 11.44 -11.92 o-xylene BTC 8 90.1 7.63 9.41 -13.7 o-xylene BTC 9 73.1 6.71 8.08 -15.07

o-xylene BTC 10 68.0 5.61 5.92 -15.38

130

Appendix Table C-42. Kd, Mass sorbed, mass removed, and cumulative mass remaining for BTEX compounds on Column 10B.

Compound Kd (L/kg) Mass sorbed (mg) Mass removed (mg)

Cum. mass remaining (mg)

Benzene BTC 1 12.8 0.92 1.09 -0.17 Benzene BTC 2 16.1 1.07 0.79 0.11 Benzene BTC 3 18.8 1.39 1.15 0.35 Benzene BTC 4 26.2 1.66 1.13 0.88 Benzene BTC 5 24.9 1.54 1.18 1.24 Benzene BTC 6 22.8 1.31 0.98 1.57 Benzene BTC 7 19.5 1.02 0.9 1.69 Benzene BTC 8 10.1 0.51 0.7 1.5 Benzene BTC 9 25.5 1.18 0.69 1.99

Benzene BTC 10 6.0 0.29 0.57 1.71 Toluene BTC 1 39.0 4.98 4.8 0.18 Toluene BTC 2 37.0 5.4 3.62 1.96 Toluene BTC 3 41.0 6.6 4.66 3.9 Toluene BTC 4 43.7 6.23 5.46 4.67 Toluene BTC 5 41.0 5.94 5.96 4.65 Toluene BTC 6 43.0 5.68 4.72 5.61 Toluene BTC 7 35.6 4.34 4.56 5.39 Toluene BTC 8 23.5 2.74 3.6 4.53 Toluene BTC 9 45.0 4.93 3.24 6.22

Toluene BTC 10 22.8 2.53 2.7 6.05 Ethylbenzene BTC 1 106.2 6.1 4.36 1.74 Ethylbenzene BTC 2 98.1 5.5 3.51 3.73 Ethylbenzene BTC 3 102.8 7.85 4.5 7.08 Ethylbenzene BTC 4 88.7 6.07 6.32 6.83 Ethylbenzene BTC 5 89.4 5.41 5.89 6.35 Ethylbenzene BTC 6 90.0 5.44 4.7 7.09 Ethylbenzene BTC 7 74.6 4.55 5.02 6.62 Ethylbenzene BTC 8 58.5 3.23 3.88 5.97 Ethylbenzene BTC 9 79.3 4.01 3.08 6.9 Ethylbenzene BTC 10 55.8 2.68 2.35 7.23 p-&m-xylene BTC 1 113.6 4.17 3.12 1.05 p-&m-xylene BTC 2 106.2 4.64 3 2.69 p-&m-xylene BTC 3 108.2 5.5 3.27 4.92 p-&m-xylene BTC 4 97.4 4.52 5.12 4.32 p-&m-xylene BTC 5 98.1 4.63 5.41 3.54 p-&m-xylene BTC 6 98.1 4.62 4.44 3.72 p-&m-xylene BTC 7 82.6 3.58 4.28 3.02 p-&m-xylene BTC 8 65.8 2.82 3.59 2.25 p-&m-xylene BTC 9 79.3 3.65 2.86 3.04 p-&m-xylene BTC 10 68.5 2.53 2.26 3.31

o-xylene BTC 1 106.2 1.54 1.39 0.15 o-xylene BTC 2 101.5 6.71 5.35 1.51 o-xylene BTC 3 102.8 8.84 6.21 4.14 o-xylene BTC 4 86.0 6.27 8.82 1.59 o-xylene BTC 5 89.4 6.64 9.55 -1.32 o-xylene BTC 6 88.0 6.08 7.07 -2.31 o-xylene BTC 7 73.9 5.13 7.71 -4.89 o-xylene BTC 8 59.1 4.03 6.58 -7.44 o-xylene BTC 9 82.0 5.1 4.8 -7.14

o-xylene BTC 10 53.8 3.02 3.46 -7.58

131

Appendix Table C-43. CXTFIT 2.1 calculations used to create manuscript Figure 2.

Sample Pore Volumes

Fitted BenzeneC/Co

Fitted Toluene C/Co

Fitted Ethyl-benzene C/Co

Fitted p-&m-xylene C/Co

Fitted o-xylene C/Co

1 2.8 0.000 0.000 0.000 0.000 0.000 2 6.7 0.047 0.000 0.000 0.000 0.000 3 10.4 0.509 0.000 0.000 0.000 0.000 4 14.5 0.862 0.003 0.000 0.000 0.000 5 18.6 0.929 0.040 0.000 0.000 0.000 6 30.3 0.939 0.520 0.000 0.000 0.001 7 41.9 0.942 0.813 0.011 0.005 0.029 8 53.4 0.945 0.867 0.083 0.047 0.149 9 64.8 0.948 0.880 0.230 0.157 0.323 10 76.0 0.951 0.887 0.389 0.302 0.467 11 87.1 0.953 0.894 0.512 0.430 0.557 12 134.1 0.962 0.919 0.700 0.661 0.685 13 207.0 0.973 0.947 0.799 0.774 0.778 14 254.0 0.978 0.959 0.844 0.825 0.823 15 307.3 0.983 0.970 0.884 0.869 0.863 16 346.4 0.986 0.976 0.906 0.895 0.887 17 389.4 0.988 0.981 0.926 0.917 0.908 18 417.0 0.990 0.984 0.937 0.929 0.920

132

APPENDIX D. BATCH EXPERIMENT RESULTS

The methods used to perform the batch experiments were summarized in the

manuscipt. This section provides the results obtained from the experiments shown in

Appendix Figures D-1 through D-5 and the data is complied in Appendix Tables D-1

through D-15. The results from the two sets of blank samples (containing BTEX but no

SMZ) show that very little volatilization loss occurs during shaking and centrifugation,

but one-third to one-half of the BTEX escapes during the transfer of supernatant to a vial

for analysis. The “% Solute Retained During Transfer” was determined by dividing the

average concentration of the “Conc. Blank with Transfer” by the average concentration

of the “Conc. Blank without Transfer” for each initial concentration level. The samples

containing SMZ were corrected for volatilization loss during transfer by dividing the

equilibrium concentration obtained from GC analysis by the average percent of solute

retained during the transfer process. Thus, assuming that the BTEX in the supernatant in

the SMZ-containing vials behaves similarly during transfer processes, the equilibrium

concentration reported in the tables below is corrected for the loss of BTEX during the

transfer prior to GC analysis. The initial solution concentration for each initial

concentration level was taken as the average of two duplicate standards that were

prepared and analyzed immediately when all other blank and SMZ-containing vials were

prepared. The concentrations of these duplicates is shown in Appendix Tables D-1

through D-15 in the left-most column.

133

Kd = 6.15 L/kgR2 = 0.93

0

10

20

30

40

50

0 2 4 6 8

C (mg/L)

S (m

g/kg

)

(a) Virgin SMZ

Kd = 6.68 L/kgR2 = 0.79

0102030405060

0 2 4 6 8

C (mg/L)

S (m

g/kg

)

(b) Columns 5A/5B SMZ

Kd = 7.29 L/kgR2 = 0.94

0102030405060

0 2 4 6 8

C (mg/L)

S (m

g/kg

)

(c) Columns 10A/10B SMZ

Appendix Figure D-1. Benzene sorption isotherm for (a) virgin SMZ; (b) Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ.

134

Kd = 14.17 L/kgR2 = 0.96

020406080

100120

0 2 4 6 8 10

C (mg/L)

S (m

g/kg

)

(a) Virgin SMZ

Kd = 15.78 L/kgR2 = 0.80

020406080

100120140

0 2 4 6 8

C (mg/L)

S (m

g/kg

)


Kd = 16.79 L/kgR2 = 0.94

020406080

100120140

0 2 4 6 8

C (mg/L)

S (m

g/kg

)


Appendix Figure D-2. Toluene sorption isotherm for (a) virgin SMZ; (b) Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ.

135

Kd = 30.22 L/kgR2 = 0.97

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5 2.0 2.5

C (mg/L)

S (m

g/kg

)

(a) Virgin SMZ

Kd = 34.52 L/kgR2 = 0.83

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5 2.0

C (mg/L)

S (m

g/kg

)


Kd = 35.67 L/kgR2 = 0.93

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5 2.0

C (mg/L)

S (m

g/kg

)


Appendix Figure D-3. Ethylbenzene sorption isotherm for (a) virgin SMZ; (b) Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ.

136

Kd = 33.58 L/kgR2 = 0.96

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5 2.0

C (mg/L)

S (m

g/kg

)

(a) Virgin SMZ

y = 37.28 L/kgR2 = 0.77

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5

C (mg/L)

S (m

g/kg

)


Kd = 38.63 L/kgR2 = 0.88

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5 2.0

C (mg/L)

S (m

g/kg

)


Appendix Figure D-4. p-&m-xylene sorption isotherm for (a) virgin SMZ; (b) Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ.

137

Kd = 35.52 L/kgR2 = 0.97

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5 2.0

C (mg/L)

S (m

g/kg

)

(a) Virgin SMZ

Kd = 40.81 L/kgR2 = 0.81

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5

C (mg/L)

S (m

g/kg

)


Kd = 41.79 L/kgR2 = 0.92

0

10

20

30

40

50

60

70

0.0 0.5 1.0 1.5

C (mg/L)

S (m

g/kg

)


Appendix Figure D-5. o-xylene sorption isotherm for (a) virgin SMZ; (b) Columns 5A/5B SMZ; and (c) Columns 10A/10B SMZ.

138

Appendix Table D-1. Benzene sorption on virgin SMZ.

Initial Conc. (mg/L)

Equil. Conc. (mg/L)

Amt. Solute Sorbed (mg/kg)

Conc. Blank with Transfer (mg/L)

Conc. Blank without Transfer (mg/L)

% Solute Retained During Transfer

3.54 1.70 9.87 2.33 3.73 0.60 3.88 1.61 10.13 2.47 4.32 6.95 2.84 19.46 4.14 6.14 0.67 no data 3.04 18.89 4.27 6.41 9.37 4.29 25.55 5.82 9.50 0.64 9.70 4.40 25.21 6.02 8.88 12.34 7.57 40.69 7.69 11.62 0.64 12.63 5.04 35.16 7.17 11.62 15.84 6.24 44.61 10.27 15.14 0.64 15.62 7.08 42.13 9.26 15.25 Average: 0.64

Appendix Table D-2. Benzene sorption on Column 5A/5B SMZ.


Equil. Conc. (mg/L)





3.61 1.74 9.26 2.34 3.93 0.60 3.58 1.75 9.24 2.35 3.95 6.51 2.95 17.11 4.20 6.84 0.62 6.37 3.53 15.40 4.35 7.01 10.95 5.59 24.90 6.34 no data 0.65 9.70 4.54 28.00 5.95 9.42 12.74 5.23 35.45 7.41 12.61 0.61 12.65 5.13 35.76 7.88 no data 15.67 5.99 50.27 9.72 15.36 0.63 18.25 6.15 49.79 9.70 15.65 Average 0.62

139

Appendix Table D-3. Benzene sorption on Column 10A/10B SMZ.


Equil. Conc. (mg/L)





3.35 1.94 8.72 2.51 3.94 0.62 3.86 1.81 9.11 2.43 4.02 6.65 2.73 18.94 4.00 6.50 0.60 6.82 2.85 18.56 no data 6.79 9.74 4.15 28.45 5.64 9.57 0.60 10.58 3.69 29.81 5.85 9.69 12.95 5.22 36.29 7.77 13.04 0.62 12.85 5.32 36.00 7.71 12.09 17.78 6.03 48.96 9.12 15.47 0.60 15.55 6.23 48.38 9.25 14.96 Average 0.61

Appendix Table D-4. Toluene sorption on virgin SMZ.


Equil. Conc. (mg/L)





8.10 2.15 27.16 4.84 8.27 0.57 8.63 1.89 27.91 5.12 9.16 14.77 3.35 49.25 8.28 13.14 0.62 no data 3.42 49.04 8.39 13.71 19.80 4.87 65.54 11.33 19.40 0.61 20.11 4.86 65.57 11.66 18.53 25.50 8.01 105.64 14.87 23.87 0.60 26.16 5.47 87.26 13.74 24.10 32.23 6.83 109.12 19.24 30.99 0.60 32.34 7.88 106.03 17.81 31.14 Average: 0.60

140

Appendix Table D-5. Toluene sorption on Column 5A/5B SMZ.


Equil. Conc. (mg/L)





8.25 2.11 26.56 4.85 8.56 0.57 8.12 2.08 26.65 4.83 8.57 14.08 3.22 46.08 8.30 14.19 0.59 13.68 3.72 44.61 8.68 14.73 22.59 6.05 68.37 12.32 no data 0.60 20.46 4.94 71.61 11.43 19.74 25.69 5.56 86.93 14.51 25.70 0.58 25.93 5.31 87.67 15.13 no data 32.13 5.99 119.06 18.56 31.22 0.59 36.19 6.22 118.39 18.58 31.94 Average: 0.58

Appendix Table D-6. Toluene sorption on Column 10A/10B SMZ.


Equil. Conc. (mg/L)





7.68 2.41 25.47 5.12 8.57 0.58 8.59 2.10 26.37 4.91 8.57 14.06 2.98 48.22 7.89 13.79 0.57 14.42 3.07 47.96 no data 14.09 19.99 4.52 70.25 10.67 19.82 0.55 21.76 3.86 72.18 11.20 19.92 26.24 5.42 89.42 15.18 26.37 0.59 26.42 5.55 89.05 14.87 24.78 34.96 6.27 115.30 17.53 31.44 0.57 31.89 6.48 114.68 17.76 30.27 Average: 0.57

141

Appendix Table D-7. Ethylbenzene sorption on virgin SMZ.


Equil. Conc. (mg/L)





2.92 0.52 10.34 1.54 2.91 0.52 3.01 0.37 10.77 1.62 3.12 6.21 0.75 22.64 3.14 5.58 0.55 no data 0.74 22.66 3.08 5.79 9.16 1.21 33.32 4.57 8.71 0.54 9.27 1.14 33.52 4.70 8.41 12.09 1.89 57.01 6.20 11.06 0.53 12.38 1.32 45.08 5.67 11.22 15.55 1.79 57.31 8.01 14.87 0.52 15.73 1.97 56.78 7.55 14.86 Average: 0.53

Appendix Table D-8. Ethylbenzene sorption on Column 5A/5B SMZ.


Equil. Conc. (mg/L)






142

Appendix Table D-9. Ethylbenzene sorption on Column 10A/10B SMZ.


Equil. Conc. (mg/L)





2.79 0.60 9.97 1.63 3.01 0.53 3.07 0.42 10.49 1.54 2.98 6.07 0.68 22.62 3.02 5.90 0.51 6.24 0.66 22.68 no data 5.94 9.07 1.07 34.68 4.19 8.89 0.49 9.84 0.87 35.28 4.47 8.95 12.20 1.30 45.58 6.34 12.10 0.53 12.50 1.29 45.62 6.17 11.60 16.44 1.57 59.93 7.63 15.13 0.51 15.84 1.57 59.93 7.71 14.67 Average: 0.51

Appendix Table D-10. p-&m-xylene sorption on virgin SMZ.


Equil. Conc. (mg/L)





4.08 0.63 14.79 2.17 4.05 0.54 4.24 0.47 15.28 2.30 4.28 7.34 0.83 26.95 3.78 6.58 0.56 no data 0.79 27.06 3.73 6.82 10.09 1.21 36.95 5.09 9.46 0.55 10.17 1.12 37.22 5.22 9.24 12.97 1.81 60.34 6.81 11.80 0.55 13.26 1.27 48.72 6.18 12.00 16.32 1.70 60.66 8.50 15.49 0.54 16.51 1.84 60.25 8.02 15.39 Average: 0.55

143

Appendix Table D-11. p-&m-xylene sorption on Column 5A/5B SMZ.


Equil. Conc. (mg/L)






Appendix Table D-12. p-&m-xylene sorption on Column 10A/10B SMZ.


Equil. Conc. (mg/L)





3.93 0.73 14.28 2.29 4.13 0.54 4.28 0.52 14.89 2.15 4.08 7.10 0.74 26.47 3.55 6.86 0.52 7.22 0.71 26.57 no data 6.83 9.97 1.10 38.28 4.71 9.79 0.50 10.78 0.88 38.92 5.01 9.73 13.01 1.28 48.87 6.92 12.81 0.54 13.31 1.26 48.95 6.75 12.36 17.01 1.49 62.57 7.96 15.60 0.52 16.46 1.47 62.63 8.10 15.14 Average: 0.52

144

Appendix Table D-13. o-xylene sorption on virgin SMZ.


Equil. Conc. (mg/L)





3.21 0.50 11.54 2.05 3.22 0.64 3.30 0.35 11.98 2.15 3.39 6.51 0.69 24.00 4.00 5.92 0.66 no data 0.66 24.08 3.91 6.10 9.43 1.08 34.69 5.75 8.98 0.66 9.49 1.00 34.92 5.89 8.78 12.36 1.63 58.80 7.71 11.48 0.64 12.64 1.15 46.61 7.11 11.62 15.83 1.59 58.94 9.84 15.13 0.63 15.96 1.71 58.56 9.36 15.22 Average: 0.64

Appendix Table D-14. o-xylene sorption on Column 5A/5B SMZ.


Equil. Conc. (mg/L)






145

Appendix Table D-15. o-xylene sorption on Column 10A/10B SMZ.


Equil. Conc. (mg/L)





3.08 0.57 11.22 2.15 3.27 0.64 3.37 0.39 11.76 2.05 3.25 6.30 0.61 23.78 3.84 6.19 0.62 6.49 0.58 23.86 no data 6.22 9.27 0.94 36.00 5.25 9.17 0.59 10.10 0.75 36.54 5.56 9.18 12.37 1.13 46.93 7.99 12.53 0.64 12.76 1.10 47.04 7.86 12.13 16.49 1.40 60.95 9.73 15.93 0.62 16.04 1.37 61.05 9.83 15.43 Average: 0.62

146

APPENDIX E. FIELD COLUMN METHODS AND RESULTS

The methods used to perform the field experiments were summarized in the

manuscript. This section provides a more thorough explanation of these methods, and the

results obtained from the experiments.

In addition to the field-scale SMZ treatment system discussed in the manuscript,

we operated a second field column while the primary column was undergoing

regeneration. This second column was only operated with virgin SMZ and was not

regenerated. The objective for the second column was to provide a means to continue to

treat produced water while the primary field column was undergoing regeneration. The

second field column was smaller than the primary column, with a radius of 305 mm and a

length of 1120 mm. The available volume of this column was approximately 68 L. The

system contained approximately 100 mm of headspace and held 60 kg of 14-40 mesh

SMZ.

The smaller column was in operation for approximately 45 hours. The initial flow rate

during this run was 95 L/hr (2.6 PV/hr). However, as with the larger column, there was a

drop in flow rate as the trial progressed, dropping to 47 L/hr (1.3 PV/hr) at the end of the

run. A large increase in BTEX influent concentrations occurred during the last 36 hours

of operation. It is believed that these elevated measurements were caused by the

discharge of one or more trucks carrying produced water with these high BTEX levels

into the separation tanks. During this run, BTEX levels fluctuated within the following

ranges: benzene 20-36 mg/L, toluene 32-61 mg/L, ethylbenzene 2-20 mg/L, p-&m-

147

xylene 17-79 mg/L, o-xylene 4-41 mg/L. The BTC for the smaller field column is shown

in Appendix Figure E-1.

Appendix Table E-1 contains the BTC data on virgin SMZ in the larger field

column, Appendix Table E-2 contains the BTC data on regenerated SMZ in the larger

field column, Appendix Table E-3 contains the BTC data on virgin SMZ in the smaller

field column, and Appendix Table E-4 provides the air-sparging data for the larger field

column.

148


0

0.2

0.4

0.6

0.8

1C

/C0

BenzeneTolueneEthylbenzenep-&m-xyleneo-xylene

Appendix Figure E-1. Observed BTEX breakthrough on virgin SMZ in smaller field column.

149

Appendix Table E-1. Data for BTEX BTC on virgin SMZ in larger field column.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

1 0.4 0.000 0.000 0.000 0.000 0.000 2 1.7 0.000 0.000 0.000 0.000 0.000 3 2.6 0.000 0.001 0.000 0.000 0.000 6 4.9 0.001 0.000 0.000 0.000 0.000 7 5.7 0.003 0.000 0.000 0.000 0.000 8 6.5 0.007 0.000 0.000 0.000 0.000 9 8.2 0.011 0.001 0.000 0.000 0.000 11 11.9 0.173 0.023 0.000 0.000 0.000 12 13.8 0.204 0.023 0.000 0.000 0.000 14 17.6 0.616 0.170 0.000 0.001 0.000 15 19.5 0.675 0.206 0.000 0.001 0.000 16 21.5 0.709 0.256 0.000 0.001 0.000 19 27.4 0.788 0.339 0.000 0.002 0.003 20 29.3 0.800 0.369 0.000 0.002 0.003 22 33.3 0.775 0.402 0.000 0.018 0.003 24 37.2 0.792 0.445 0.002 0.002 0.005 25 39.1 0.831 0.498 0.003 0.003 0.006 26 41.4 0.704 0.414 0.002 0.003 0.005 28 45.5 0.632 0.389 0.003 0.003 0.005 29 47.6 0.872 0.546 0.005 0.004 0.008 30 49.6 0.808 0.551 0.005 0.004 0.008 31 51.7 0.814 0.568 0.006 0.004 0.010 32 53.7 0.774 0.548 0.005 0.004 0.009 35 59.5 0.793 0.566 0.007 0.005 0.011 36 62.8 0.820 0.593 0.009 0.006 0.015 37 64.9 0.829 0.611 0.011 0.007 0.017 38 66.8 0.835 0.617 0.011 0.007 0.018 39 68.5 0.803 0.599 0.011 0.007 0.018 41 72.8 0.733 0.578 0.012 0.008 0.019 43 78.9 0.806 0.592 0.012 0.008 0.021 44 81.5 0.783 0.574 0.012 0.008 0.020

150

Appendix Table E-2. Data for BTEX BTC on regenerated SMZ in larger field column.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

80 0.6 0.028 0.124 0.097 0.091 0.153 81 2.3 0.018 0.118 0.085 0.083 0.142 83 6.1 0.011 0.127 0.085 0.091 0.157 84 7.8 0.011 0.125 0.075 0.084 0.133 85 9.8 0.043 0.111 0.072 0.080 0.130 86 11.4 0.012 0.126 0.091 0.090 0.152 87 13.3 0.244 0.111 0.093 0.099 0.164 89 17.0 0.342 0.098 0.103 0.107 0.172 90 19.1 0.409 0.107 0.113 0.121 0.192 92 23.9 0.511 0.125 0.139 0.165 0.233 93 26.9 0.570 0.139 0.139 0.148 0.230 94 29.1 0.554 0.119 0.119 0.128 0.201 95 31.4 0.500 0.091 0.105 0.119 0.173 96 34.1 0.590 0.113 0.120 0.143 0.209 97 36.2 0.585 0.128 0.117 0.138 0.190 101 45.6 0.787 0.222 0.103 0.107 0.164 103 49.5 0.886 0.314 0.157 0.167 0.248 105 53.2 0.850 0.304 0.122 0.138 0.199 107 56.9 0.833 0.419 0.135 0.151 0.211 110 65.2 0.578 0.405 0.075 0.080 0.121

151

Appendix Table E-3. Data for BTEX BTC on virgin SMZ in smaller field column.

Sample Pore Volumes

BenzeneC/Co

Toluene C/Co

Ethyl-benzene C/Co

p-&m-xylene C/Co

o-xylene C/Co

45 0.2 0.000 0.000 0.000 0.000 0.000 47 5.7 0.002 0.003 0.000 0.000 0.000 48 8.1 0.007 0.009 0.000 0.000 0.000 49 11.2 0.005 0.006 0.000 0.000 0.000 50 13.6 0.011 0.007 0.000 0.000 0.000 52 19.9 0.065 0.004 0.000 0.000 0.000 55 27.5 0.171 0.009 0.000 0.000 0.000 57 32.3 0.283 0.041 0.000 0.000 0.000 58 34.7 0.374 0.097 0.000 0.001 0.000 59 37.5 0.540 0.223 0.001 0.001 0.001 60 41.1 0.478 0.222 0.001 0.001 0.001 62 46.7 0.478 0.233 0.001 0.001 0.001 63 50.0 0.359 0.194 0.001 0.001 0.001 64 53.2 0.523 0.342 0.002 0.003 0.003 65 56.6 0.532 0.353 0.002 0.003 0.003 66 59.6 0.535 0.398 0.003 0.004 0.004 67 62.6 0.471 0.337 0.002 0.003 0.003 68 65.1 0.518 0.347 0.003 0.003 0.006 69 66.9 0.564 0.435 0.006 0.006 0.010 70 68.3 0.595 0.451 0.008 0.006 0.061 71 70.5 0.663 0.498 0.011 0.008 0.016 72 73.3 0.659 0.498 0.013 0.008 0.017 73 75.6 0.756 0.552 0.016 0.011 0.022 74 78.3 0.749 0.552 0.017 0.012 0.024 76 82.7 0.704 0.544 0.019 0.013 0.024 77 84.6 0.774 0.599 0.026 0.017 0.033 78 86.5 0.787 0.608 0.028 0.017 0.036 79 88.3 0.762 0.592 0.029 0.017 0.035

Appendix Table E-4. BTEX removal data from 14-inch field column during air sparging.

Sample

Pore Volumes


Benzene Mass Removed (g)

Toluene Conc. (mg/L)

Toluene Mass Removed (g)

Ethyl-benzene Conc. (mg/L)

Ethyl-benzene Mass Rem. (g)


p-&m-xylene Mass Rem. (g)


o-xylene Mass Removed (g)

1 16.3 2.541 2.159 3.174 2.696 0.269 0.229 0.313 0.266 0.408 0.347 2 40.6 1.809 4.464 2.813 6.281 0.131 0.395 0.186 0.503 0.219 0.626 3 65.0 1.269 6.081 2.640 9.646 0.073 0.489 0.122 0.659 0.114 0.772 4 91.0 0.449 6.691 1.105 11.148 0.025 0.523 0.047 0.723 0.037 0.822 5 119.5 0.369 7.240 1.186 12.911 0.029 0.565 0.059 0.810 0.038 0.878 6 148.0 0.287 7.666 1.130 14.592 0.028 0.607 0.068 0.911 0.042 0.940 7 172.3 0.320 8.074 1.393 16.366 0.039 0.657 0.089 1.024 0.055 1.010 8 196.7 0.263 8.410 1.394 18.143 0.048 0.718 0.119 1.176 0.069 1.097 9 225.2 0.132 8.606 0.778 19.300 0.028 0.760 0.069 1.278 0.047 1.167 10 253.6 0.138 8.811 0.931 20.684 0.037 0.815 0.097 1.421 0.058 1.252 11 279.6 0.095 8.940 0.745 21.697 0.034 0.860 0.092 1.546 0.055 1.327 12 305.7 0.096 9.071 0.803 22.788 0.039 0.913 0.108 1.694 0.065 1.416 13 334.1 0.041 9.133 0.376 23.346 0.021 0.945 0.064 1.790 0.040 1.476 14 362.6 0.048 9.204 0.471 24.047 0.026 0.984 0.081 1.909 0.050 1.551 15 419.5 0.043 9.333 0.434 25.335 0.026 1.062 0.079 2.144 0.051 1.702 16 476.4 0.030 9.422 0.374 26.448 0.027 1.143 0.088 2.406 0.058 1.876 17 533.3 0.017 9.472 0.243 27.170 0.022 1.208 0.071 2.617 0.050 2.023 18 590.2 0.009 9.498 0.140 27.586 0.015 1.251 0.066 2.812 0.047 2.164 19 655.2 0.011 9.537 0.219 28.330 0.025 1.336 0.092 3.124 0.068 2.394 20 704.0 0.005 9.551 0.047 28.450 0.006 1.350 0.098 3.374 0.074 2.582 21 785.3 0.005 9.574 0.140 29.046 0.019 1.429 0.075 3.693 0.058 2.830 22 798.8 0.013 9.583 0.315 29.268 0.044 1.460 0.173 3.816 0.132 2.924 23 820.5 0.012 9.596 0.290 29.597 0.045 1.511 0.176 4.015 0.136 3.078

152

153

APPENDIX F. ADDITIONAL ORGANIC MATERIAL IN PRODUCED WATER

The produced water from the field site in Wyoming contained numerous organic

compounds. Untreated water collected during the field test in July 2002 was analyzed by

an independent lab (DHL Analytical, Round Rock, TX) for TOC with a result of 470

mg/L. The analysis of the produced water collected for the laboratory experiments was

presented in the manuscript with a TOC result of 1000 mg/L. BTEX levels were

approximately 80 mg/L, meaning a significant number of organic compounds in the

water were not quantified during analysis. The untreated water sample collected during

the field test was also analyzed by DHL Analytical for total petroleum hydrocarbons

(TPH) and semi-volatile components. The results of this analysis are presented in

Appendix Table F-1.

Appendix Table F-1. TPH and semi-volatile analysis of untreated produced water collected during

field testing (only noting compounds present above detectable limits).

Analysis Result (mg/L) TPH Range: C6-C12 129 TPH Range: >C12-C28 8.24 2,4- Dimethylphenol 0.816 2-Methylnaphthalene 0.160 2-Methylphenol 1.35 4-Methylphenol 1.00 Dibenzofuran 0.0044 Fluorene 0.0046 Naphthalene 0.164 Phenanthrene 0.0038 Phenol 0.764

154

The identity of the remaining unaccounted organic compounds is difficult to

determine. A list of organic components that may exist in the produced water used in this

study can be constructed based on compounds identified from other produced waters.

Witter and Jones (1999) reported the following organic components of produced water

from seven samples at a California oil-processing facility: heterocyclic polysulfides,

butanoic acids, pentanoic acids, hexanoic acids, heptanoic acids, phenols, benzene,

toluene, xylenes, 3-thiophene carboxaldehyde, benzenemethanethiol, N,N-dimethyl-

aninododecane, and other unknown compounds. The sum of all measured organic

compounds ranged from 0.93 to 57.8 mg/L in the seven samples collected. McCormack

et al. (2001) identified a range of polar organic compounds in produced water from the

North Sea including imidazolines, alkylbenzene sulfonates, quaternary ammonium

compounds, and ethoxylates. Specific compounds identified included linear

alkylbenzenesulfonates, alkyldimethylbenzylammonium compounds, 2-alkyl-1-

ethylamine-2-imidazolines, 2-alkyl-1-[N-ethylalkylamide]-2-imidazolines and a di-

[alkyldimethylammonium-ethyl]ether.

Many of the compounds discussed above are polar, which are not attracted to

SMZ like neutral compounds such as BTEX are. If many of the unidentified organic

compounds are polar, a significant portion of the TOC in produced water will pass

through the SMZ system without being removed. Effluent samples from the laboratory

column experiments were analyzed for TOC to determine how much organic material

was removed from the produced water. The samples for this test were collected

following the completion of a sorption cycle from the reservoir containing all effluent

water from the cycle. The results from this test are shown in Appendix Table F-2. These

155

results show that a significant portion of TOC passes through the column, and one

effluent sample (9th effluent) has a higher TOC than the influent water. These results

indicate that many organic compounds present in the produced water are polar

compounds. This conclusion is supported by Jacobs et al. (1992), who determined that

polar compounds represent 84% of total organic compounds in effluent produced water in

the North Sea.

Appendix Table F-2. TOC analysis of produced water used in laboratory column experiments.

Sample TOC (mg/L) Influent 1000 Column 10A 3rd sorption cycle effluent 950 Column 10A 6th sorption cycle effluent 990 Column 10A 9th sorption cycle effluent 1200

To determine which semi-volatile compounds were removed from SMZ during

the field tests, a sample of effluent water was collected for semi-volatile analysis from the

smaller field column at 2.4 PV. Appendix Table F-3 shows the results of the influent

semi-volatile analysis (also shown in Appendix Table F-1) and the 2.4 PV effluent semi-

volatile analysis. These results show that many semi-volatile compounds are completely

retained by SMZ at early time while the concentration of other compounds is reduced by

two orders of magnitude. One compound, benzyl alcohol, was present in the effluent

concentration but not in the influent concentration. The reason for this is most likely

because the influent sample was not collected at the same time as the effluent sample, and

benzyl alcohol was not present at the time the influent sample was collected. Produced

water from the region the field site is located in was constantly being delivered to the site

and the produced water composition in the separation tanks could have been changing

with each additional water delivery.

156

Appendix Table F-3. Semi-volatile breakthrough at 2.4 PV from smaller field column.

Analysis Influent Conc. (mg/L)

Effluent Conc. (mg/L)

2,4- Dimethylphenol 0.816 Not Detected 2-Methylnaphthalene 0.160 0.0038 2-Methylphenol 1.35 0.0184 4-Methylphenol 1.00 Not Detected Benzyl Alcohol Not Detected 0.0086 Dibenzofuran 0.0044 Not Detected Fluorene 0.0046 Not Detected Naphthalene 0.164 Not Detected Phenanthrene 0.0038 Not Detected Phenol 0.764 Not Detected

One additional method was utilized to monitor the organic compounds present in

produced water during the field tests. A photoionization detector (described in the

manuscript) was used to record the concentration of volatile organic compounds (VOC)

in headspace above influent and effluent water samples. To collect samples for this

analysis, 2.5 L glass bottles were filled to the same level (approximately 1/3 full) and the

headspace in these bottles was sampled with the photoionization detector. The

breakthrough curves for VOC are shown in Appendix Figures F-1, F-2, and F-3 for virgin

SMZ in the smaller field column, virgin SMZ in the larger field column, and regenerated

SMZ in the larger field column, respectively. The two plots containing virgin SMZ data

(Appendix Figures F-1, F-2) show that the effluent VOC concentration increases rapidly

shortly after toluene breakthrough. This can be explained because toluene composes a

significant portion of the VOC in this produced water. The VOC breakthrough on

regenerated SMZ occurs shortly before toluene breakthrough. This could be caused by

the incomplete air-sparging of many VOC (including toluene), concentrating them at the

effluent end of the column and releasing them in effluent water at earlier time. This is

consistent with the observations of ethylbenzene and xylenes in early effluent water

157

samples on regenerated SMZ, even though no ethylbenzene or xylenes was present in the

effluent water from virgin SMZ treatment. The data used to construct these figures are

shown in Appendix Tables F-1, F-2, and F-3, respectively.

Future work should be performed to identify what hazardous components are

present in produced water that are not removed by SMZ. The TOC results presented in

this appendix show that many organic compounds do pass through the SMZ system, but

that BTEX and many of the semi-volatiles are retained in the system.

158

0.0

0.2

0.4

0.6

0.8

1.0

0 10 20 30 40 50 60 70 80 90 100

Pore Volumes

C/C

oBenzeneTolueneEthylbenzenep&m xyleneo-xyleneVOC

Appendix Figure F-1. PID measurements with BTEX BTCs on virgin SMZ in smaller field column.

159

0.0

0.2

0.4

0.6

0.8

1.0

0 10 20 30 40 50 60 70 80 90 100

Pore Volumes

C/C

o

Benzene

Toluene

Ethylbenzene

p&m xylene

o-xylene

VOC

Appendix Figure F-2. PID measurements with BTEX BTCs on virgin SMZ in larger field column.

160

0.0

0.2

0.4

0.6

0.8

1.0

0 10 20 30 40 50 60 70 80 90 100

Pore Volumes

C/C

o

Benzene

Toluene

Ethylbenzene

p&m xylene

o-xylene

VOC

Appendix Figure F-3. PID measurements with BTEX BTCs on regenerated SMZ in larger field column.

161

Appendix Table F-4. PID measurements recorded on virgin SMZ in smaller field column.

VOC influent (ppm) VOC effluent (ppm) C/C0 Pore Volumes 700 3 0.004 0.210 600 3 0.005 8.099 650 25 0.038 19.932 640 250 0.391 27.504

1300 85 0.065 34.709 800 110 0.138 37.470

1500 300 0.200 53.151 1100 300 0.273 56.648 990 160 0.162 65.150 520 300 0.577 70.470 850 150 0.176 75.589 900 400 0.444 84.569 500 300 0.600 86.541

162

Appendix Table F-5. PID measurements recorded on virgin SMZ in larger field column.

VOC influent (ppm) VOC effluent (ppm) C/C0

Pore Volumes

390 3.7 0.009 4.917 480 15 0.031 8.178 600 50 0.083 21.472 650 100 0.154 27.449 700 100 0.143 29.275 500 200 0.400 37.244 550 100 0.182 41.437 600 120 0.200 47.559 650 200 0.308 51.689 650 150 0.231 59.465 750 225 0.300 66.800

163

Appendix Table F-6. PID measurements recorded on regenerated SMZ in larger field column.

VOC influent (ppm) VOC effluent (ppm) C/C0 Pore Volumes 1000 70 0.070 0.580 1300 50 0.038 7.812 500 70 0.140 11.362 900 100 0.111 17.037 250 20 0.080 29.115 500 150 0.300 36.215 400 255 0.638 49.461 550 330 0.600 65.218

164

APPENDIX F REFERENCES

Jacobs, R. P. W. M., Grant, R. O. H., Kwant, J., Marquenie, J. M., and Mentzer, E.

(1992). “The composition of produced water from Shell operated oil and gas

production in the North Sea.” Produced Water, J. P. Ray and F. R. Engelhart,

eds., Plenum Press, New York, 13-21.

McCormack, P., Jones, P., Hetheridge, M. J., and Rowland, S. J. (2001). “Analysis of

oilfield produced waters and production chemicals by electrospray ionization

multi-stage mass spectrometry (ESI-MS).” Wat. Res., 35(15) 3567-3578.

Witter, A. E., and Jones, A. D. (1999). “Chemical characterization of organic constituents

from sulfide-rich produced water using gas chromatography/mass spectrometry.”

Environ. Tox. and Chem., 18(9) 1920-1926.

165

APPENDIX G. APPLICABLE PRODUCED WATERS FOR AN SMZ

TREATMENT SYSTEM

The manuscript and appendices presented in this document have shown the

applicability of surfactant-modified zeolite in a produced-water treatment system. SMZ

successfully removes BTEX, semi-volatiles, and other VOC from produced water, but

many other organic compounds and inorganic salts pass through the system. Therefore,

the usefulness of SMZ in a standalone treatment system is best in locations where the

influent water has a low salinity or in locations where the salinity of the effluent water is

allowed to be high, such as at offshore locations. An SMZ-based treatment system could

also be combined with other treatment systems, such as reverse-osmosis, that require the

removal of some organic compounds before treatment. The use of SMZ for removal of

organic contaminants may be limited by what additional organic compounds are present

in the produced water. SMZ does not effectively remove polar organic compounds from

water and may not lower overall TOC significantly, although it does remove BTEX and

some other hazardous compounds. If these additional organic compounds are of

regulatory concern, the use of SMZ for treatment may not be the best option.

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